JP2008069104A - Method for producing helicene derivatives, triyne derivatives, and helicene derivatives - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a helicene derivative having an extremely stable helical asymmetry, equipped with a large optical anisotropy and expected to be developed in various uses, a method for producing the same and a triyne derivative becoming an intermediate of the same. <P>SOLUTION: This helicene derivative is expressed by formula (I) [wherein, at least one side of X<SP>1</SP>, Y<SP>1</SP>and X<SP>2</SP>, Y<SP>2</SP>are each present and the X<SP>1</SP>, X<SP>2</SP>, Y<SP>1</SP>, Y<SP>2</SP>are each independently any of CH<SB>2</SB>, C=O, O, N, S, P, B and Si; also the N, S, P, B and Si may be connected with any of the CH<SB>2</SB>, C=O and O; and E<SP>1</SP>, E<SP>2</SP>are each independently any of H, an alkyl, an aryl, an allyl, benzyl, an alkenyl, an akynyl, an alkyl ether, an alkyl ester, an alkyl ketone, a heterocyclic ring or the derivative of them]. The compound is produced by cyclotrimerizing a triyne derivative by using a specific rhodium compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a helicene derivative, a triyne derivative, and a helicene derivative. More specifically, [7] helicene derivatives having extremely stable helical asymmetry and high optical anisotropy, triyne derivatives serving as intermediates of the [7] helicene derivatives, and production of the [7] helicene derivatives Regarding the method.

  Organic compounds have been used in our lives as pharmaceuticals, agricultural chemicals, fragrances, food additives and the like. In recent years, organic compounds have also been used as functional organic materials such as organic EL and organic semiconductors, and practical examples such as biaryl compounds and disulfide compounds have been reported. In the future, the need for functional organic materials is expected to increase further, and various studies are being conducted in various fields.

  Among these functional organic materials, helicene derivatives are attracting great interest as new functional organic materials. Such a helicene derivative is considered to exhibit functions and physical properties based on a non-planar π-conjugated system because it has a helical structure in which a plurality of aromatic rings are condensed with an ortho group so as to form an arc. Specifically, since the helicene derivative is also a chiral molecule in which an optical isomer exists depending on the direction of the helix, the molecule itself can be a chiral chromophore. In addition, since the optically active helicene derivative exhibits a very large specific rotation, application to a detector or the like is expected by utilizing this property.

  In addition, the helicene derivative has a structure in which aromatics are closely overlapped with each other, and there is a great interest in the interaction between π electrons generated thereby. Helicene derivatives are expected to be applied to nonlinear optical materials using these properties, etc., and applied to optical devices such as molecular recognition materials, organic EL elements, fluorescent materials, organic buffer layer constituent materials, and nonlinear optical materials. Is expected.

  As a method for synthesizing a helicene derivative, a photocyclization reaction is widely known. For example, it is often synthesized through complicated multi-steps such as photocyclization of an aromatic compound synthesized by a Wittig reaction or a Siegrist reaction ( For example, see Non-Patent Document 1.) Also, a method of photocyclization by irradiating microwaves is known (see, for example, Patent Document 1). On the other hand, as a direct enantioselective synthesis method without using a photocyclization reaction, a method using a nickel complex catalyst or the like as a synthesis method of a helicene derivative by an intramolecular [2 + 2 + 2] cycloaddition reaction using a transition metal complex catalyst. A method for synthesizing enantioselective optically active helicene derivatives using a Ni (0) / (S) -MOP complex catalyst has been reported (for example, see Non-Patent Document 2).

JP-A-2005-15427 ([Claims]) “The Journal of Organic Chemistry” (USA), American Chemical Society, 1991, 56, 3769. “Tetrahedron Letters” (USA), Elsevier, 1999, 40, 1993-1996.

  By the way, among the helicene derivatives, [7] helicene derivatives have extremely stable helical asymmetry (also referred to as helicity) and can be expected to have large optical anisotropy. On the other hand, the photocyclization reaction, which is widely known as a method for synthesizing a helicene derivative, is difficult to apply to mass synthesis due to the necessity of high dilution conditions, and [7] As a means for producing a helicene derivative Was also not suitable. Also, the synthesis method using a nickel complex or the like was not satisfactory in terms of yield and enantioselectivity. In addition, the nickel complex has a problem that it is an air-unstable complex, cannot be applied to the synthesis of [7] helicene or more, and can only use a monodentate ligand.

  As other synthesis methods, those by Diels-Alder reaction, cross-coupling reaction, etc. have been reported. However, these synthesis methods have low yields and are not satisfactory in terms of substrate generality. As described above, since it is very difficult to synthesize optically active helicene derivatives in large quantities, there has been a strong demand for the development of synthetic methods that are highly enantioselective, highly efficient, and have high substrate generality.

  The present invention has been made in view of the above problems, and has a very stable helical asymmetry and a large optical anisotropy. Therefore, it can be expected to be used in various applications. [7] Helicene derivatives, [7] [7] It is an object to provide a method for producing a helicene derivative capable of producing a helicene derivative with high enantioselectivity in a stable and high yield, and a triyne derivative as an intermediate.

  In order to solve the above problems, a helicene derivative according to claim 1 of the present invention is represented by the following formula (I).

（式（Ｉ）中、Ｘ^１とＹ^１、Ｘ^２とＹ^２は、それぞれ、いずれか少なくとも一方が存在し、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２は、それぞれ独立してＣＨ_２、Ｃ＝Ｏ、Ｏ、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉのいずれかを示す。また、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉは、ＣＨ_２、Ｃ＝Ｏ、Ｏのいずれかと結合されていてもよい。Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (I), at least one of X ¹ and Y ¹ , X ² and Y ² is present, respectively, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.)

  A helicene derivative according to claim 2 of the present invention is characterized in that, in claim 1, it is represented by the following formula (II).

（式（II）中、Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (II), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)

The helicene derivative according to claim 3 of the present invention is the helicene derivative according to claim 1 or 2, wherein the E ¹ and / or E ² are each independently a hydrogen atom, an alkyl group, an alkyl ether group, an alkyl ester group, It is one kind selected from the group consisting of alkyl ketone groups.

  The triyne derivative according to claim 4 of the present invention is represented by the following formula (III).

（式（III）中、Ｘ^１とＹ^１、Ｘ^２とＹ^２は、それぞれ、いずれか少なくとも一方が存在し、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２は、それぞれ独立してＣＨ_２、Ｃ＝Ｏ、Ｏ、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉのいずれかを示す。また、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉは、ＣＨ_２、Ｃ＝Ｏ、Ｏのいずれかと結合されていてもよい。Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (III), at least one of X ¹ and Y ¹ , X ² and Y ² is present, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.)

  The triyne derivative according to claim 5 of the present invention is represented by the following formula (IV) in claim 4.

（式（IV）中、Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In Formula (IV), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)

  The method for producing a helicene derivative according to claim 6 of the present invention is characterized in that a triyne derivative represented by the following formula (III) is cyclized and trimerized using a rhodium compound represented by the following formula (X). And

（式（Ｘ）中、ＬはＲ^１Ｒ^２Ｐ−Ｑ−ＰＲ^３Ｒ^４で表されるビスホスフィンを表し、Ｙは非共役ジエン化合物を表し、ＸはＢＦ_４、ＰＦ_６、ＢＰｈ_４、ＣｌＯ_４、ＳｂＦ_６またはＣＦ_３ＳＯ_３を表す。また、ｍは１または２を表し、ｎは０または１を表す。ただし、ｍ＝１のとき、ｎは０または１を表し、ｍ＝２のときはｎ＝０を表す。Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して置換基を有していてもよいアリール基、置換基を有してもよいシクロアルキル基を表し、Ｑは置換基を有していてもよい２価のアリーレン基を表す。）

(In formula (X), L represents a bisphosphine represented by R ¹ R ² PQ-PR ³ R ⁴ , Y represents a non-conjugated diene compound, X represents BF ₄ , PF ₆ , BPh ₄ , Represents ClO ₄ , SbF ₆ or CF ₃ SO ₃ , m represents 1 or 2, n represents 0 or 1, provided that when m = 1, n represents 0 or 1 and m = 2 In this case, n represents 0. R ¹ , R ² , R ³ and R ⁴ each independently represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent. Q represents a divalent arylene group which may have a substituent.

（式（III）中、Ｘ^１とＹ^１、Ｘ^２とＹ^２は、それぞれ、いずれか少なくとも一方が存在し、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２は、それぞれ独立してＣＨ_２、Ｃ＝Ｏ、Ｏ、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉのいずれかを示す。また、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉは、ＣＨ_２、Ｃ＝Ｏ、Ｏのいずれかと結合されていてもよい。Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (III), at least one of X ¹ and Y ¹ , X ² and Y ² is present, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.)

  The method for producing a helicene derivative according to claim 7 of the present invention is characterized in that, in claim 6, the triyne derivative is represented by the following formula (IV).

（式（IV）中、Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In Formula (IV), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)

The helicene derivative according to claim 1 of the present invention is characterized in that π electrons form a chiral helical structure, becomes an optically active [7] helicene derivative, has excellent specific rotation, and expands the π electron system. Have. In addition, since a 5-membered or 6-membered ring containing X ¹ and Y ¹ and a 5- or 6-membered ring containing X ² and Y ² are formed in the helicene derivative, It has the feature that various physical properties can be expected by the introduction, and various organic devices such as organic EL elements, fluorescent materials, organic buffer layer constituent materials, nonlinear optical materials, optically active ligands, etc. as functional organic materials It can be applied to various uses such as optically active column packing material.

In the helicene derivative according to claim 2 of the present invention, as represented by the formula (II), X ¹ and X ² in the helicene derivative according to the formula (I) are —O—, Y ¹ and Y ² are —CH— Since it is _2- , there are merits that the synthesis is very easy, the π-electron system is expanded, and the helical structure is relatively stable to acids and bases.

The helicene derivative according to claim 3 of the present invention has a dipole moment increased by using E ¹ and E ² constituting the helicene derivative as specific groups, and the application development as a functional organic material is expanded. There are benefits.

  Since the triyne derivative according to claim 4 of the present invention has a structure represented by the formula (III), a suitable intermediate for producing the helicene derivative of the present invention represented by the above formula (I) Become.

In the triyne derivative according to claim 5 of the present invention, in the triyne derivative according to the above formula (III), X ¹ and X ² are represented by —O—, Y ¹ , as represented by the formula (IV), Since Y ² is specified as —CH ₂ —, it is a suitable intermediate for producing the helicene derivative of the present invention represented by the above formula (II).

  In the method for producing a helicene derivative according to claim 6 of the present invention, the triyne derivative represented by the formula (III) is cyclized and trimerized using the rhodium compound represented by the formula (X). Therefore, the helicene derivative of the present invention represented by the above formula (I) can be produced in a large amount with high yield and high enantioselectivity. In addition, since the reaction can be allowed to proceed at room temperature, the helicene derivative having the above characteristics can be efficiently produced by a simple operation.

  The method for producing a helicene derivative according to claim 7 of the present invention specifies the triyne derivative used in the method for producing a helicene derivative according to claim 6 as represented by the formula (IV). While enjoying the effect which the manufacturing method of this invention show | plays, the triyne derivative represented by Formula (II) can be manufactured efficiently.

  Hereinafter, the helicene derivative of the present invention, the triyne derivative serving as an intermediate of the helicene derivative, and the method for producing the helicene derivative will be specifically described. The helicene derivative of the present invention is represented by the following formula (I).

  The helicene derivative represented by the formula (I) becomes an optically active [7] helicene derivative in which π electrons form a chiral helical structure. As described above, the [7] helicene derivative has extremely stable helical asymmetry and can be expected to have a large optical anisotropy, so that the π-electron system with excellent specific rotation is expanded. Etc.

Here, in the formula (1), X ¹ and Y ¹ , X ² and Y ² are each at least one (one or both of X ¹ and Y ¹ , and one of X ² and Y ^2). Or both), and X ¹ , X ² , Y ¹ , and Y ² each independently represent CH ₂ , C═O, O, N, S, P, B, or Si. N, S, P, B, and Si may be bonded to any one of CH ₂ , C═O, and O. Thus, in the helicene derivatives represented in formula (I), X ¹ and Y ¹ may be either at least one of existence, when one of X ¹ and Y ¹ is present Is a helicene derivative of formula (I) in which a 5-membered ring containing X ¹ or Y ¹ is formed, and when both X ¹ and Y ¹ are present, A 6-membered ring containing X ¹ and Y ¹ will be formed. Similarly, in the helicene derivatives represented in formula (I), X ² and Y ² may be either at least one of existence, when one of X ² and Y ² are present In the helicene derivative of the formula (I), a 5-membered ring containing X ² or Y ² is formed, and when both X ² and Y ² are present, the helicene derivative of the formula (I) A 6-membered ring containing ² and Y ² will be formed.

In the present invention, a 5-membered or 6-membered ring containing X ¹ and Y ¹ and a 5-membered or 6-membered ring containing X ² and Y ² are formed in the helicene derivative. Therefore, there is a merit that various physical properties can be expected by introducing hetero atoms.

In formula (I), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl Examples thereof include ketone groups, heterocyclic groups, and derivatives thereof. These may have not only a straight chain structure but also a side chain, and may further have a cyclic structure. E ¹ and E ² are particularly preferably each independently a hydrogen atom, an alkyl group, an alkyl ether group, an alkyl ester group, or an alkyl ketone group, and by specifying such a group, the dipole moment Will increase the use of functional organic materials.

Examples of the alkyl group include a methyl group (CH ₃ —), an ethyl group (CH ₃ CH ₂ —), a propyl group (CH ₃ CH ₂ CH ₂ —), and an isopropyl group ((CH ₃ ) ₂ CH—). , Butyl group (CH ₃ CH ₂ CH ₂ CH ₂ —), isobutyl group ((CH ₃ ) ₂ CHCH ₂ —), s-butyl group (CH ₃ CH ₂ CH (CH ₃ ) —), t-butyl group ( (CH ₃ ) ₃ C—), phenyl group (C ₆ H ₅ —) and the like can be mentioned.

The helicene derivative of the present invention is represented by the following formula (II) when X ¹ and X ² are —O—, Y ¹ and Y ² are —CH ₂ — in formula (I).

（式（II）中、Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (II), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)

  In order to produce a helicene derivative represented by the formula (I), a triyne derivative represented by the following formula (III) is cyclized and trimerized in the presence of a rhodium compound represented by the following formula (X). [2 + 2 + 2] cycloaddition. In the present invention, [2 + 2 + 2] cycloaddition is an example of acetylene, and as shown below, three triple bonds are cyclized to form a 6-membered ring to form a benzene skeleton. It is something to be made.

（式（III）中、Ｘ^１とＹ^１、Ｘ^２とＹ^２は、それぞれ、いずれか少なくとも一方が存在し、Ｘ^１、Ｘ^２、Ｙ^１、Ｙ^２は、それぞれ独立してＣＨ_２、Ｃ＝Ｏ、Ｏ、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉのいずれかを示す。また、Ｎ、Ｓ、Ｐ、Ｂ、Ｓｉは、ＣＨ_２、Ｃ＝Ｏ、Ｏのいずれかと結合されていてもよい。Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In formula (III), at least one of X ¹ and Y ¹ , X ² and Y ² is present, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.)

  Hereinafter, the rhodium compound used in the method for producing a helicene derivative of the present invention will be described. The rhodium compound is represented by the following formula (X).

（式（Ｘ）中、ＬはＲ^１Ｒ^２Ｐ−Ｑ−ＰＲ^３Ｒ^４で表されるビスホスフィンを表し、Ｙは非共役ジエン化合物を表し、ＸはＢＦ_４、ＰＦ_６、ＢＰｈ_４、ＣｌＯ_４、ＳｂＦ_６またはＣＦ_３ＳＯ_３を表す。また、ｍは１または２を表し、ｎは０または１を表す。ただし、ｍ＝１のとき、ｎは０または１を表し、ｍ＝２のときはｎ＝０を表す。Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立して置換基を有していてもよいアリール基、置換基を有してもよいシクロアルキル基を表し、Ｑは置換基を有していてもよい２価のアリーレン基を表す。）

(In formula (X), L represents a bisphosphine represented by R ¹ R ² PQ-PR ³ R ⁴ , Y represents a non-conjugated diene compound, X represents BF ₄ , PF ₆ , BPh ₄ , Represents ClO ₄ , SbF ₆ or CF ₃ SO ₃ , m represents 1 or 2, n represents 0 or 1, provided that when m = 1, n represents 0 or 1 and m = 2 In this case, n represents 0. R ¹ , R ² , R ³ and R ⁴ each independently represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent. Q represents a divalent arylene group which may have a substituent.

In the formula (X), the bisphosphine represented by R ¹ R ² PQ-PR ³ R ⁴ represented by L has a substituent represented by R ¹ , R ² , R ³ and R ^4. Examples of the aryl group that may be used include aryl groups having 6 to 14 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. These aryl groups may have a substituent, and examples of the substituent include an alkyl group, an alkoxyl group, an aryl group, and a heterocyclic group.

  The alkyl group may be linear, branched or cyclic, and examples thereof include an alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. Examples of the alkoxyl group may be linear, branched or cyclic, and examples thereof include an alkoxyl group having 1 to 6 carbon atoms, specifically, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n -Butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group and the like.

  As an aryl group, a C6-C14 aryl group is mentioned, for example, Specifically, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group etc. are mentioned. Examples of the heterocyclic group include an aliphatic heterocyclic group and an aromatic heterocyclic group, and the aliphatic heterocyclic group has, for example, 2 to 14 carbon atoms and at least one hetero atom, preferably 1 to 3 hetero atoms. For example, a 5- to 8-membered, preferably 5- or 6-membered monocyclic, polycyclic or condensed ring aliphatic heterocyclic group containing a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom can be mentioned. Specific examples of the aliphatic heterocyclic group include pyrrolidyl-2-one group, piperidino group, piperazinyl group, morpholino group, tetrahydrofuryl group, tetrahydropyranyl group, tetrahydrothienyl group and the like. The aromatic heterocyclic group has, for example, 2 to 15 carbon atoms and contains at least one, preferably 1 to 3 hetero atoms such as nitrogen, oxygen and sulfur atoms as hetero atoms, 5 to 8 A 5-membered, preferably 5- or 6-membered monocyclic, polycyclic or condensed ring heteroaryl group, specifically, a furyl group, a thienyl group, a pyridyl group, a pyrimidyl group, a pyrazyl group, a pyridazyl group, Pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalyl group, phthalazyl group, quinazolyl group, naphthyridyl group, cinnolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl Groups and the like.

Examples of the cycloalkyl group which may have a substituent represented by R ¹ , R ² , R ³ and R ⁴ include a 5-membered or 6-membered cycloalkyl group. The alkyl group or alkoxyl group may be substituted by 1 to 2 or more. Preferred cycloalkyl groups include a cyclopentyl group and a cyclohexyl group.

  Examples of the divalent arylene group represented by Q include a phenylene group, a biphenyldiyl group, a binaphthalenediyl group, and the like. Examples of the phenylene group include o or m-phenylene group, and the phenylene group includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. An alkyl group such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group and tert-butoxy group; hydroxyl group, amino group or substituted amino group Etc. may be substituted. As the biphenyldiyl group and the binaphthalenediyl group, those having a 1,1′-biaryl-2,2′-diyl type structure are preferable, and the biphenyldiyl group and the binaphthalenediyl group are alkyl groups as described above, It may be substituted with an alkoxyl group, for example, an alkylenedioxy group such as a methylenedioxy group, an ethylenedioxy group, or a trimethylenedioxy group, a hydroxyl group, an amino group, a substituted amino group, or the like.

Specific examples of bisphosphine represented by L, that is, R ¹ R ² PQ-PR ³ R ⁴ include, for example, bisphosphines known per se, and one of them is represented by the following formula (Y). And the compounds represented.

（式（Ｙ）中、Ｒ^１１及びＲ^１２は、それぞれ独立して、アルキル基、アルコキシル基もしくはハロゲン原子で置換されていてもよいフェニル基、シクロペンチル基、またはシクロヘキシル基を示す）

(In formula (Y), R ¹¹ and R ¹² each independently represents an alkyl group, an alkoxyl group, or a phenyl group, a cyclopentyl group, or a cyclohexyl group, which may be substituted with a halogen atom)

Examples of the alkyl group for the substituent of the phenyl group in R ¹¹ and R ¹² include linear or branched alkyl groups having 1 to 6 carbon atoms such as a methyl group and a tert-butyl group; For example, a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group and a tert-butoxy group; examples of the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom.

Specific examples of R ¹¹ and R ¹² include, for example, phenyl group, p-tolyl group, m-tolyl group, 3,5-xylyl group, p-tert-butylphenyl group, p-methoxyphenyl group, p-chlorophenyl. Group, cyclopentyl group, cyclohexyl group and the like.

  The binaphthyl ring, which is the basic skeleton of the compound represented by the formula (Y), is an alkyl group such as a methyl group or a tert-butyl group; an alkoxyl group such as a methoxy group or a tert-butoxy group; a trimethylsilyl group or a triisopropylsilyl group. And a trialkylsilyl group such as a tert-butyldimethylsilyl group and a triarylsilyl group such as a triphenylsilyl group.

Moreover, the compound represented by the following general formula (Z) is mentioned as another specific example of the bisphosphine represented by R < ¹ > R < ² > PQ-PR < ³ > R < ⁴ >.

（式（Ｚ）中、Ｒ^１３及びＲ^１４は、それぞれ独立して、アルキル基、アルコキシル基もしくはハロゲン原子で置換されていてもよいフェニル基、シクロペンチル基またはシクロヘキシル基を示す。Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、それぞれ独立して、水素原子、アルキル基、アルコキシル基、アシルオキシ基、ハロゲン原子、ハロアルキル基またはジアルキルアミノ基を示し、Ｒ^１５、Ｒ^１６及びＲ^１７のうちの２つで置換基を有していてもよいメチレン鎖または置換基を有していてもよいモノまたはポリメチレンジオキシ基を形成していてもよく、また、Ｒ^１８、Ｒ^１９及びＲ^２０の内の２つで置換基を有していてもよいメチレン鎖または置換基を有していてもよいモノまたはポリメチレンジオキシ基を形成していてもよい。ただし、Ｒ^１７とＲ^２０が共に水素原子の場合は除く。）

(In Formula (Z), R ¹³ and R ¹⁴ each independently represent an alkyl group, an alkoxyl group, or a phenyl group, a cyclopentyl group, or a cyclohexyl group that may be substituted with a halogen atom. R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, an acyloxy group, a halogen atom, a haloalkyl group or a dialkylamino group, and R ¹⁵ , R ¹⁶ and R 20 Two of ¹⁷ may form a methylene chain which may have a substituent or a mono or polymethylenedioxy group which may have a substituent, and R ¹⁸ , R ¹⁹ and two in substituted optionally also have a good methylene chain or substituent mono- or polymethylene of the R ²⁰ dioxabicycloctane It may form a group. However, in the case of R ¹⁷ and R ²⁰ are both hydrogen atoms excluded.)

Examples of the alkyl group for the substituent of the phenyl group in the above R ¹³ and R ¹⁴ include, for example, a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group and a tert-butyl group, and an alkoxyl group. For example, a linear or branched alkoxy group having 1 to 6 carbon atoms such as a methoxy group or a tert-butoxy group, and a halogen atom include, for example, a chlorine atom, a bromine atom, a fluorine atom, and the like. Multiple substitutions may be made on the phenyl group. Specific examples of R ¹³ and R ¹⁴ include, for example, phenyl group, p-tolyl group, m-tolyl group, o-tolyl group, 3,5-xylyl group, 3,5-di-tert-butylphenyl group, Examples include p-tert-butylphenyl group, p-methoxyphenyl group, 3,5-di-tert-butyl-4-methoxyphenyl group, p-chlorophenyl group, m-fluorophenyl group, cyclopentyl group, cyclohexyl group and the like. .

Examples of the alkyl group in R ^{15 to} R ²⁰ include a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group and a tert-butyl group; examples of the alkoxyl group include a methoxy group, linear or branched alkoxyl groups having 1 to 6 carbon atoms such as a tert-butoxy group; examples of the acyloxy group include 2 carbon atoms such as an acetoxy group, a propanoyloxy group, a trifluoroacetoxy group, and a benzoyloxy group A halogen atom, for example, a chlorine atom, a bromine atom, a fluorine atom, etc .; a haloalkyl group, for example, a haloalkyl group having 1 to 4 carbon atoms, such as a trifluoromethyl group; Examples thereof include a dimethylamino group and a diethylamino group. Examples of the methylene chain when two of R ¹⁵ , R ¹⁶ and R ¹⁷ form a methylene chain, and the case where two of R ¹⁸ , R ¹⁹ and R ²⁰ form a methylene chain include: A methylene chain having 3 to 5 carbon atoms is preferred, and specific examples include a trimethylene group, a tetramethylene group, and a pentamethylene group. In addition, examples of the substituent of the methylene chain which may have a substituent include an alkyl group and a halogen atom, and specific examples of the substituent include, for example, an alkyl as described above having 1 to 6 carbon atoms. Group, fluorine atom and the like.

In addition, when two of R ¹⁵ , R ¹⁶ and R ¹⁷ form a mono- or polymethylenedioxy group which may have a substituent, and two of R ¹⁸ , R ¹⁹ and R ²⁰ Specific examples of forming a mono- or polymethylenedioxy group which may have a substituent include, for example, a methylenedioxy group, an ethylenedioxy group, and a trimethylenedioxy group. Examples of the substituent substituted on the mono- or polymethylenedioxy group include an alkyl group and a halogen atom. Specific examples of the substituent of the mono- or polymethylenedioxy group which may have a substituent Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms and a fluorine atom.

  In the formula (X), the non-conjugated diene compound represented by Y may be cyclic or non-cyclic. When the non-conjugated diene compound is a cyclic non-conjugated diene compound, monocyclic, polycyclic, condensed cyclic, Any of a crosslinked ring may be used. The non-conjugated diene compound may be a non-conjugated diene compound substituted with a substituent, that is, a substituted non-conjugated diene compound. The substituent is not particularly limited as long as it does not adversely affect the production method of the present invention. Preferred examples of the non-conjugated diene compound include 1,5-cyclooctadiene, bicyclo [2,2,1] hepta-2,5-diene, 1,5-hexadiene, and the like.

  The rhodium compound represented by the formula (X) used in the present invention can be obtained by a known method in an inert gas atmosphere or commercially available rhodium-, for example, as shown in Scheme 1 below. After reacting the olefin coordination complex with the above-mentioned bisphosphine represented by L in an organic solvent such as methanol, ethanol, isopropanol, butanol, toluene and tetrahydrofuran, MX (M is a monovalent metal cation). X represents the same meaning as described above), or the counter anion exchange reaction is carried out (rhodium compound (A) or (B)), or hydrogen gas is further reacted to remove the olefinic ligand. (Rhodium compound (C)). (In the formula, COD represents 1,5-cyclooctadiene. The same shall apply hereinafter.)

(Scheme 1)

  As shown in the following scheme 2, the rhodium compound represented by the formula (X) used in the present invention is a bisphosphine represented by L in a rhodium-bisolefin complex that has been subjected to a counter anion exchange reaction in advance. It can also be obtained by reacting and subsequently desorbing the olefinic ligand with hydrogen gas.

(Scheme 2)

  At this time, the addition amount of bisphosphine represented by L with respect to the number of moles of the central metal of the rhodium-olefin coordination complex is 1.0 to 2.4 times mole because a part of bisphosphine may be oxidized. More preferably, it is desirable to use 1.05 to 2.2 times mole.

As the rhodium-olefin coordination complex used for the production of the rhodium compound represented by the formula (X), various complexes can be handled depending on the selection of the olefin ligand. [Rh (COD) Cl] ₂ which is a rhodium complex of 1,5-cyclooctadiene and [Rh (NBD) Cl] ₂ which is a rhodium complex of norbornadiene
(In the formula, NBD represents 2,5-norbornadiene. The same shall apply hereinafter). The catalytically active species of the present invention is [Rh (L)] X, but the precursor rhodium compound (A) can also be used in the method for producing a helicene derivative of the present invention.

  In the counter anion exchange reaction, for example, it is preferable to react with a silver salt (AgX) in terms of handling.

  The rhodium compounds (A), (B) and (C) can be used in the production method of the present invention without any particular purification after preparation.

  The method for producing helicene of the present invention is carried out by reacting a rhodium compound represented by the formula (X) or a solution containing the rhodium compound with a triyne derivative represented by the formula (III), for example.

  Specifically, first, the rhodium compound represented by the formula (X) or a solution containing the rhodium compound is added to the reaction solvent (or the reaction solvent is added to the rhodium compound or the solution containing the rhodium compound). By adding a triyne derivative represented by the formula (III), the reaction proceeds, the triyne derivative is cyclized and trimerized, an asymmetric [2 + 2 + 2] cycloaddition reaction proceeds, and the helicene represented by the formula (I) Derivatives are synthesized.

  The reaction solvent is not particularly limited as long as it does not participate in the reaction. For example, amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, dichloromethane, 1,2-dichloroethane, chloroform , Halogenated hydrocarbons such as carbon tetrachloride and o-dichlorobenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and cyclohexane, for example, aromatic hydrocarbons such as benzene, toluene and xylene , Non-nucleophilic alcohols such as tert-butanol, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dimethoxyethane, ethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane Kind and Sulfoxides such as methyl sulfoxide. Each of these solvents may be used alone or in combination of two or more. Furthermore, in some cases, alkynes themselves may be used as a reaction solvent.

  The amount of the rhodium compound used may normally be about 1 to 50 mol% with respect to the triyne derivative of the reaction substrate. The reaction is preferably performed in an inert gas such as nitrogen or argon.

  The reaction temperature may be appropriately determined depending on the type of triyne derivative used and the like, but may be carried out at about -20 ° C to 80 ° C. In the production method of the present invention, since the reaction can proceed even at room temperature, a helicene derivative can be obtained by a simple operation.

  The reaction time may be appropriately determined depending on the amounts of the triyne derivative and rhodium compound used, but is usually 10 minutes to 200 hours, preferably 1 hour to 50 hours.

  After completion of the reaction, post-treatment operations that are usually performed in this kind of field such as filtration and silica gel column chromatography are performed, and the desired helicene can be obtained by combining purification methods such as crystallization, distillation, and various chromatography alone or in combination as appropriate. Derivatives can be obtained.

Next, an example of a means for producing a triyne derivative represented by formula (III), which is an intermediate in the production of a helicene derivative represented by formula (I), is represented by formula (V) as a starting material. -Using iodo-2-naphthol, a binaphthol derivative (di (2-hydroxynaphthalen-1-yl) acetylene) represented by the following formula (V-5) is produced, and using such a binaphthol derivative, The means for producing the triyne derivative represented by the formula (IV) will be described. The triyne derivative represented by the formula (IV) is ^one in which X ¹ and X ² are —O— and Y ¹ and Y ² are —CH ₂ — in the formula (III). It is used as an intermediate of the represented helicene derivative.

（式（IV）中、Ｅ^１、Ｅ^２は、それぞれ独立して水素原子、アルキル基、アリール基、アリル基、ベンジル基、アルケニル基、アルキニル基、アルキルエーテル基、アルキルエステル基、アルキルケトン基、複素環基またはこれらの誘導体のいずれかを示す。）

(In Formula (IV), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)

  First, sodium hydride (NaH) is allowed to act on 1-iodo-2-naphthol represented by the formula (V) as a starting material, and reacted with methoxymethyl chloride having a MOM group (MOM-Cl). 1-iodo-2-methoxymethoxynaphthalene represented by the formula (V-1) is obtained.

  In the synthesis of 1-iodo-2-methoxymethoxynaphthalene, it is preferable to protect the hydroxyl group using an MOM group. Since the bacterial head coupling and the deprotection of the trimethylsilyl group are performed under basic conditions in a later step, it is preferable to select a MOM group that is strong against bases and relatively easy to protect and deprotect.

  Next, 1-iodo-2-methoxymethoxynaphthalene (formula (V-1)) and trimethylsilylacetylene are coupled to each other, and (2-methoxymethoxynaphthalene-1 represented by formula (V-2) is represented. 1-ethynyl 2 represented by the formula (V-3), which is a terminal alkyne by deprotection of the trimethylsilyl group of (2-methoxymethoxynaphthalen-1-ylethynyl) trimethylsilane -Synthesize methoxymethoxynaphthalene.

  This terminal alkyne, 1-ethynyl-2-methoxymethoxynaphthalene, and the previously synthesized 1-iodo-2-methoxymethoxynaphthalene (formula (V-1)) were subjected to bacterial head coupling and protected with the MOM group The di (2-methoxymethoxynaphthalen-1-yl) acetylene represented by the formula (V-4) is synthesized. Further, by deprotecting the MOM group in this di (2-methoxymethoxynaphthalen-1-yl) acetylene in the presence of hydrochloric acid, a binaphthol derivative represented by the formula (V-5) (di (2-hydroxynaphthalene- 1-yl) acetylene) can be obtained.

  From the binaphthol derivative (di (2-hydroxynaphthalen-1-yl) acetylene) represented by the formula (V-5) obtained according to the above contents, it is represented by the formula (IV) described above as a general formula. Can be synthesized. For example, the triyne derivative (IV-1) having an ether bond in the linker can be synthesized by an etherification reaction of di (2-hydroxynaphthalen-1-yl) acetylene and propargyl bromide. Such a triyne derivative can be used as an intermediate for producing a helicene derivative represented by the formula (II-1).

  In addition, a triyne derivative (IV-) having an ether bond in a linker by an etherification reaction of di (2-hydroxynaphthalen-1-yl) acetylene represented by the formula (V-5) and 1-bromo-2-butyne. 2) can be synthesized. Such a triyne derivative can be used as an intermediate for producing a helicene derivative represented by the formula (II-2).

  Here, when the temperature was raised to 80 ° C. in the etherification synthesis reaction described above, the reaction became complicated, and the yield of the target triyne was lowered. Although the reactivity decreases, the reaction proceeds even at room temperature. Therefore, it is considered that the yield is improved when the reaction is performed at room temperature for a long time.

  Furthermore, from the triyne derivative (IV-1) having an alkyne at the terminal, for example, by reacting lithium acetylide generated by the action of LDA with chloromethyl methyl ether, a coordinating substituent at the alkyne terminal It is possible to synthesize a triyne derivative (IV-3) having Such a triyne derivative can be used as an intermediate for producing a helicene derivative represented by the formula (II-3).

  Similarly, a triyne derivative (IV-4) having an electron-attracting substituent at the alkyne end can be synthesized by reacting a triyne derivative (IV-1) having a terminal alkyne with methyl chloroformate. Such a triyne derivative can be used as an intermediate for producing a helicene derivative represented by the formula (II-4).

In the above description, as a method for producing a triyne derivative serving as an intermediate in the production of a helicene derivative represented by formula (I), 1-iodo-2 represented by formula (V) is used as a starting material. -A naphthol derivative (di (2-hydroxynaphthalen-1-yl) acetylene) represented by the formula (V-5) is produced using naphthol, and the binaphthol derivative is used to produce a binaphthol derivative represented by the formula (IV). Although an example of producing a triyne derivative to be produced has been described, the triyne derivative represented by the formula (III) is suitably produced by introducing X ¹ , X ² , Y ¹ , Y ² into the reaction system. can do.

As described above, the helicene derivative of the present invention represented by the formula (I) is an optically active [7] helicene derivative in which π electrons form a chiral helical structure, and has extremely stable helical asymmetry. In addition, it can be expected to have a large optical anisotropy, has an excellent specific rotation, has an extended π-electron system, and the like. Furthermore, since a 5-membered or 6-membered ring containing X ¹ and Y ¹ and a 5- or 6-membered ring containing X ² and Y ² are formed in the helicene derivative, a hetero atom It has the feature that various physical properties can be expected by the introduction of.

  Therefore, the helicene derivative of the present invention includes various organic devices such as organic EL elements, fluorescent materials, organic buffer layer constituting materials, and nonlinear optical materials, optically active ligands, optically active column fillers, and the like as functional organic materials. It can be applied as a use.

  Further, according to the method for producing a helicene derivative of the present invention in which a triyne derivative represented by formula (III) is cyclized and trimerized using a rhodium compound represented by formula (X), the formula (I) The helicene derivative of the present invention represented by the formula (1) can be produced in large quantities with high enantioselectivity and in high yield. In addition, since the reaction proceeds at room temperature as the reaction temperature, a helicene derivative having the above characteristics can be efficiently produced by a simple operation. The triyne derivative of the present invention represented by the formula (III) is also a suitable intermediate for producing the helicene derivative of the present invention represented by the aforementioned formula (I).

  The aspect described above shows one aspect of the present invention, and the present invention is not limited to the above-described embodiment, and has the configuration of the present invention and can achieve the objects and effects. It goes without saying that modifications and improvements within the scope are included in the content of the present invention. Further, the specific structure, shape, and the like in carrying out the present invention are not problematic as other structures, shapes, and the like as long as the objects and effects of the present invention can be achieved. The present invention is not limited to the above-described embodiments, and modifications and improvements within the scope that can achieve the object of the present invention are included in the present invention.

For example, as the types of helicene derivatives and triyne derivatives, the formula (II) or (II-1) to (II-4) is used as the helicene derivative, and the formula (IV), or (IV-1) to (IV) is used as the triyne derivative. Although IV-4) has been described as an example, helicene derivatives and triyne derivatives are not limited to these, and have the requirements of X ¹ , X ² , Y ¹ , Y ² , E ¹ , E ^{2 described} above. As long as the group is applied, helicene derivatives and triyne derivatives can be freely selected.
In addition, the specific structure, shape, and the like in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not restrict | limited at all by these Examples.

[Example 1]
Production of helicene derivative (1):
According to the following (1) to (8), the helicene derivative 8H, 11H-naphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran-9,10-dimethyldicarboxylate was synthesized.

(1) Synthesis of 1-iodo-2-methoxymethoxynaphthalene:
To a stirred suspension of sodium hydride (55% paraffin solution, 0.89 g, 20.5 mmol) in tetrahydrofuran (20 ml), 1-iodo-2-naphthol (5.00 g, 18 0.5 mmol) and a solution of methoxymethyl chloride (2.2 mL, 29.2 mmol) in tetrahydrofuran (30 ml) were added at room temperature, and the mixture was stirred at room temperature for 3 hours. The product after the reaction was extracted with ether. The organic layer was washed with brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (hexane: ethyl acetate = 20: 1), and 1-iodo-2-methoxymethoxynaphthalene represented by the formula (V-1) was converted into a pearl yellow liquid (2) ( 5.54 g, 17.6 mmol, 95% yield). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.16 (d, J = 8.1 Hz 1H), 7.79 (d, J = 9.0 Hz) J = 9.0 Hz, 1H), 7.75 (d , J = 8.1 Hz, 1H) 7.51-7.58 (m, 1H), 7.37-7.44 (m, 1H), 7.36 (d, J = 9.0 Hz, 1H), 5.36 (s, 2H), 3.58 (s, 3H)

(2) Synthesis of (2-methoxymethoxynaphthalen-1-ylethynyl) trimethylsilane:
Tetrakis (triphenylphosphine) was added to a diisopropylamine solution (50 ml) of 1-iodo-2-methoxymethoxynaphthalene (2.02 g, 6.42 mmol) and trimethylsilylacetylene (1.1 ml, 7.78 mmol) obtained in (1). ) Palladium (75 mg, 0.064 mmol) was added. The mixture was stirred for 5 minutes and more copper iodide (28 mg, 0.14 mmol) was added. The mixture was stirred for 5 hours at room temperature under an argon atmosphere. The brown oily product was filtered and concentrated. The crude (2-methoxymethoxynaphthalen-1-ylethynyl) trimethylsilane (formula (V-2)) 2.99 g obtained was used without purification in the next synthesis step. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.26 (d, J = 8.1 Hz, 1H), 7.73-7.80 (m, 2H), 7.55 (ddd, J = 8.1) 6.9 and 1.2 Hz, 1 H), 7.41 (ddd, J = 8.4, 8.9, and 1.2 Hz, 1 H), 7.35 (d, J = 9.0 Hz, 1 H), 5.37 (S, 2H), 3.59 (s, 3H), 0.34 (s, 9H)

(3) Synthesis of 1-ethynyl-2-methoxymethoxynaphthalene:
To 2 ml of aqueous potassium hydroxide (0.5 g) solution was added 2-methoxymethoxynaphthalen-1-ylethynyltrimethylsilane (2.99 g) obtained in (2) in methanol (20 ml) / tetrahydrofuran solution (5 ml). . The mixed solution was vigorously stirred at room temperature for 30 minutes. The reaction mixture was diluted with water (5 ml) and extracted with ether. The organic layer was washed with brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (hexane: ethyl acetate = 10: 1), and 1-ethynyl-2-methoxymethoxynaphthalene represented by the formula (V-3) was converted into a purple liquid (1.21 g, 5.7 mmol, 89% yield from 1-iodo-2-methoxymethoxynaphthalene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.29 (d, J = 8.1 Hz), 7.75-7.83 (m, 2H), 7.56 (ddd, J = 8.4, 6. 9, and 1.5 Hz, 1 H), 7.42 (d, J = 9.0 Hz, 1 H), 7.41 (ddd, J = 8.4, 6.9, and 1.5 Hz, 1 H), 5.39. (S, 2H), 3.73 (s, 1H), 3.57 (s, 3H)

(4) Synthesis of di (2-methoxymethoxynaphthalen-1-yl) acetylene:
Tetra (triphenylphosphine) palladium (0.011 g, 0.01 mmol) was added to a diisopropylamine solution (30 ml) of 1-iodo-2-methoxymethoxynaphthalene (0.150 g, 0476 mmol) obtained in (1). did. The mixture was stirred for 5 minutes and more copper iodide (10 mg, 0.05 mmol) was added. Then, 1-ethynyl-2-methoxymethoxynaphthalene (0.100 g, 0.471 mmol) obtained in (3) was slowly added to the mixture solution. The mixture was stirred at room temperature for 3 hours under an argon atmosphere. Further, after filtration, the filtrate was concentrated and purified by silica gel chromatography (hexane: ethyl acetate = 10: 1). The di (2-methoxymethoxynaphthalen-1-yl) acetylene represented by the formula (V-4) was converted into a yellow solid from the 1-ethynyl 2-methoxymethoxynaphthalene obtained in (3) in a yield of 82%. Obtained. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.64 (d, J = 8.1 Hz, 2H), 7.79-7.86 (m, 4H), 7.60 (ddd, J = 8.1) 6.9, and 0.9 Hz, 2H), 7.41-7.48 (m, 4H), 5.51 (s, 4H), 3.63 (s, 6H)

(5) Synthesis of di (2-hydroxynaphthalen-1-yl) acetylene:
Tetrahydrofuran / water / hydrochloric acid solution of di (2-methoxymethoxynaphthalen-1-yl) acetylene (1.04 g, 2.60 mmol) obtained in (4) (18 ml, volume ratio 12: 4: 2) Was stirred at room temperature for 21 hours. The product was extracted with ethyl acetate. The organic layer was washed, the organic layer was washed with brine, dried over sodium sulfate and concentrated. The crude product is purified by silica gel chromatography (hexane: ethyl acetate = 10: 1) to obtain di (2-hydroxynaphthalen-1-yl) acetylene represented by the formula (V-5) as a yellow solid. (0.731 g, 2.36 mmol, 60% yield from di (2-methoxymethoxynaphthalen-1-yl) acetylene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.27 (d, J = 8.1 Hz, 2H), 7.81-7.87 (m, 4H), 7.60 (ddd, J = 8.1) 6.9 and 0.9 Hz, 2H), 7.43 (ddd, J = 8.1, 6.9, and 0.9 Hz, 2H), 7.27 (d, J = 9.0 Hz, 2H), 6.46 (S, 2H)

(6) Synthesis of triyne (di (2-prop-2-ynyloxynaphthalen-1-yl) acetylene):
To an acetone solution of potassium carbonate (0.461 g, 3.36 mmol), di (2-hydroxynaphthalen-1-yl) acetylene (0.206 g, 0.664 mmol) obtained in (5) and propargyl bromide (0 .242 g, 2.03 mmol) was added and the mixture was stirred at room temperature for 47 hours. The product was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (hexane: ethyl acetate = 30: 1), and di (2-prop-2-ynyloxynaphthalen-1-yl) acetylene represented by the formula (VI-1). Was obtained as a pale yellow solid (0.154 g, 0399 mmol, 60% yield from di (2-hydroxynaphthalenyl-1-yl) acetylene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.67 (d, J = 8.1 Hz, 2H), 7.80-7.89 (m, 4H), 7.63 (ddd, J = 8.1) 6.9, and 1.2 Hz, 2H), 7.46 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H), 7.42 (d, J = 9.0 Hz, 2H), 5 .07 (d, J = 2.4 Hz, 4H), 2.61 (t, J = 2.4 Hz, 2H)

(7) Synthesis of triyne (di [2- (4-methoxy-4-oxobut-2-ynyloxy) naphthalen-1-yl] acetylene:
A diisopropylamine lithium solution composed of n-butyllithium (1.52M, hexane solution, 0.45 ml, 0.68 mmol) and diisopropylamine (0.1 ml, 0.708 mmol) tetrahydrofuran solution is in a stirred state ( 6) The di (2-prop-2-ynyloxynaphthalen-1-yl) acetylene (0.115 g, 0.296 mmol) obtained in 6) was added to a tetrahydrofuran solution (10 ml) at −80 ° C. for 30 minutes. Stir. The above mixed solution was added to stirred methyl chloroformate (methyl chloroformate) (0.096 ml, 1.24 mmol) at −80 ° C., and the mixed solution was stirred at room temperature for 3 hours. The reaction was stopped by adding water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate and concentrated. The residual product was purified by silica gel chromatography (hexane: ethyl acetate = 10: 1) and di [2- (4-methoxy-4-oxobut-2-ynyloxy) naphthalene- represented by the formula (IV-4) 1-yl] acetylene was obtained as a yellow solid (0.087 g, 0.173 mmol, 58% yield from di (2-prop-2-ynyloxynaphthalen-1-yl) acetylene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.61 (d, J = 8.1 Hz, 2H), 7.87 (d, J = 9.0 Hz, 2H), 7.85 (d, J = 7. 8Hz, 2H), 7.67 (ddd, J = 8.1, 6.9, and 1.2Hz, 2H), 7.48 (ddd, J = 7.8, 6.9, and 1.2Hz, 2H) 7.36 (d, J = 9.0 Hz, 2H), 5.18 (s, 4H), 3.77 (s, 6H)

(8) Helicene (8H, 11H-naphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] Synthesis of pyran-9,10-dimethyldicarboxylate):
Under an argon atmosphere, the ligand (R, R) -Me-Duphos 3.1 mg (0.010 mmol) represented by the formula (A) and [Rh (cod) ₂ ] BF ₄ (cod: 1,5-cycloocta Diene) 4.1 mg (0.010 mmol) was added to 1.0 ml of methylene chloride solution and dissolved, and the resulting mixture was stirred under atmospheric hydrogen atmosphere for 30 minutes and then concentrated to dryness. A solution of 25.1 mg (0.05 mmol) of di [2- (4-methoxy-4-oxobut-2-ynyloxy) naphthalen-1-yl] acetylene obtained in (7) as a concentrated residue at room temperature in methylene chloride solution 0. An additional 5 ml was added and rinsed with 1.5 ml of methylene chloride solution. The mixture was stirred at room temperature for 5 hours, then concentrated to remove the solvent, and purified by thin layer chromatography (TLC) to obtain 8H, 11H-naphtho [2, represented by the formula (II-4). 1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran-9,10-dimethyldicarboxylate 12.5 mg (0.0249 mmol, yield 50%, 70% ee) was obtained. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.46 (d, J = 9.0 Hz, 2H), 7.26 (d, J = 9.0 Hz, 2H), 7.20 (d, J = 8. 1 Hz, 2H), 6.81 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H), 6.76 (d, J = 8.1 Hz, 2H), 6.58 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H). 5.54 (d, J = 13.8 Hz, 2H), 4.89 (d, J = 13.8 Hz, 2H), 3.99 (s, 6H)

[Example 1-2]
Production of helicene derivatives (1-2)
In the same manner as in Example 1 except that (R) -BINAP represented by the formula (B) is used as the ligand in Example 1 (8), 8H, 11H-naphtho [2,1-b] is used. Naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran-9,10-dimethyldicarboxylate with a yield of 38%, 42 % Ee).

[Example 2]
Production of helicene derivative (2):
Implemented except that (tri (2-prop-2-ynyloxynaphthalen-1-yl) acetylene) obtained in Example 1 (6) was used as the triyne derivative and (R) -BINAP was used as the ligand. Analogously to Example 1 (8), 8H, 11H-naphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [ 3 ′, 4 ′: 5,6] benzo- [d] pyran was obtained in a yield of 50% and 36% ee. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.47 (d, J = 9.0 Hz, 2H), 7.31 (s, 2H), 7.30 (d, J = 7.8 Hz, 2H), 7 .23 (d, J = 9.0 Hz, 2H), 6.90 (d, J = 8.1 Hz, 2H), 6.78 (ddd, J = 7.8, 6.9, and 0.9 Hz, 2H ), 6.52 (ddd, J = 8.1, 6.9, and 0.9 Hz, 2H), 5.27 (d, J = 12.0 Hz, 2H), 4.88 (d, J = 12. 0Hz, 2H)

[Example 3]
Production of helicene derivative (3):
According to the following (1) and (2), the helicene derivative 8H, 11H-9,10-dimethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′ , 4 ′: 5,6] benzo- [d] pyran was synthesized.

(1) Synthesis of triyne (di (2-but-2-ynyloxynaphthalen-1-yl) acetylene):
To 20 ml of an acetone solution of potassium carbonate (0.237 g, 1.72 mmol), di (2-hydroxynaphthalen-1-yl) acetylene (0.091 g, 0.293 mmol) obtained in Example 1 (5) and 1-Bromo-2-butyne (0.122 g, 0.914 mmol) was added and the mixture was refluxed at room temperature for 8 hours. The product was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate and concentrated. The crude product was purified by silica gel chromatography (hexane: ethyl acetate = 10: 1), and di (2-but-2-ynyloxynaphthalen-1-yl) acetylene represented by the formula (IV-2). Was obtained as a yellow solid (0.029 g, 0.0700 mmol, 24% yield from di (2-hydroxynaphthalen-1-yl) acetylene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.68 (d, J = 8.4 Hz, 2H), 7.84 (d, J = 9.0 Hz, 2H), 7.82 (d, J = 7. 8 Hz, 2H), 7.61 (ddd, J = 8.4, 6.9, and 1.2 Hz, 2H), 7.44 (ddd, J = 7.8, 6.9, and 1.2 Hz, 2H) 7.42 (d, J = 9.0 Hz, 2H), 5.00 (q, J = 2.4 Hz, 4H), 1.89 (t, J = 2.4 Hz, 6H)

(2) Helicene (8H, 11H-9, 10-dimethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] Synthesis of benzo- [d] pyran):
Similar to Example 1 (8) except that di (2-but-2-ynyloxynaphthalen-1-yl) acetylene obtained in (1) as triyne and (R) -BINAP as the ligand are used. And 8H, 11H-9,10-dimethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 represented by the formula (II-2) ': 5,6] benzo- [d] pyran was obtained with a yield of 50% and 26% ee. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.41 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 8.7 Hz, 2H), 7.20 (d, J = 8. 1 Hz, 2H), 6.91 (d, J = 8.1 Hz, 2H), 6.77 (ddd, J = 8.1, 6.9, and 0.9 Hz, 2H), 6.53 (ddd, J = 8.1, 6.9, and 0.9 Hz, 2H), 5.58 (d, J = 12.9 Hz, 2H), 4.73 (d, J = 12.9 Hz, 2H), 2.41 ( s, 6H)

[Example 4]
Production of helicene derivative (4):
According to the following (1) and (2), the helicene derivative 8H, 11H-9,10-dimethoxymethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ', 4': 5,6] benzo- [d] pyran was synthesized.

(1) Synthesis of triyne (di [2- (4-methoxybut-2-ynyloxy) naphthalen-1-yl] acetylene):
n-Butyllithium (1.52M, hexane solution, 0.4 ml, 0.608 mmol) was obtained from di (2-prop-2-ynyloxynaphthalen-1-yl) obtained in Example 1 (6). Acetylene (0.104 g, 0.269 mmol) was added to a tetrahydrofuran solution at −80 ° C. and stirred for 30 minutes. The above mixed solution was added to stirred chloromethoxymethane (0.081 ml, 1.08 mmol) at −80 ° C. and gradually returned to room temperature. The reaction was stopped by adding water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate and concentrated. The residual product was purified by silica gel chromatography (hexane: ethyl acetate = 10: 1), and di [2- (4-methoxybut-2-ynyloxy) naphthalen-1-yl] represented by the formula (IV-3) Acetylene was obtained as a yellow solid (0.028 g, 0.059 mmol, 22% yield from di (2-prop-2-ynyloxynaphthalen-1-yl) acetylene). ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.37 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 9.0 Hz, 2H), 7.82 (d, J = 8. 1 Hz, 2H), 7.60 (ddd, J = 8.4, 6.9, and 1.2 Hz, 2H), 7.43 (ddd, J = 8.1, 6.9. And 1.2 Hz, 2H) 7.40 (d, J = 9.0 Hz, 2H), 5.04 (t, J = 1.8 Hz, 4H), 4.14 (t, J = 1.8 Hz, 4H), 3.35 ( s, 6H)

(2) Helicene (8H, 11H-9,10-dimethoxymethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6 Synthesis of benzo- [d] pyran):
Example 1 (8) except that di [2- (4-methoxybut-2-ynyloxy) naphthalen-1-yl] acetylene obtained in (1) was used as the triyne and (R) -BINAP was used as the ligand. ), (8H, 11H-9,10-dimethoxymethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] represented by the formula (II-3) Pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran) was obtained in a yield of 50% and 46% ee. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.42 (d, J = 9.0 Hz, 2H), 7.26 (d, J = 9.0 Hz, 2H), 7.19 (d, J = 7. 8 Hz, 2H), 6.85 (d, J = 8.1 Hz, 2H), 6.78 (ddd, J = 7.8, 6.6, and 0.9 Hz, 2H), 6.54 (ddd, J = 8.1, 6.6, and 0.9 Hz, 2H), 5.60 (d, J = 13.2 Hz, 2H), 4.77 (d, J = 13.2 Hz, 2H), 4.75 ( d, J = 11.4 Hz, 2H), 4.68 (d, J = 11.4 Hz.2H), 3.51 (s, 6H)

[Example 5]
Production of helicene derivative (5):
According to the following (1) and (2), (8H, 11H-naphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran-9,10-dibutyldicarboxylate).

(1) Synthesis of triyne (di [2- (4-butoxybuty-2-ynyloxy) naphthalen-1-yl] acetylene):
Di [2- (4-butoxybuty-2-ynyloxy) represented by the formula (IV-5) is prepared in the same manner as in Example 1 (7) except that butyl chloroformate is used instead of methyl chloroformate. Naphthalen-1-yl] acetylene was obtained as a yellow solid in a yield of 70%. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.63 (d, J = 7.5 Hz, 2H), 7.82-7.89 (m, 4H), 7.67 (ddd, J = 8.1) 6.6, and 1.2 Hz, 2H), 7.47 (ddd, J = 7.5, 6.6, and 0.9 Hz, 2H), 7.37 (d, J = 9.3 Hz, 2H), 5 .18 (s, 4H), 4.18 (t, J = 6.6 Hz, 4H), 1.57-1.69 (m, 4H), 1.30-1.44 (m, 4H), 0 .91 (t, 7.2 Hz, 6H)

(2) Helicene (8H, 11H-9,10-dimethoxymethylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6 Synthesis of benzo- [d] pyran):
In the same manner as in Example 1 (8) except that di [2- (4-butoxybuty-2-ynyloxy) naphthalen-1-yl] acetylene obtained in (1) was used as triyne, the compound of formula (II-5 (8H, 11H-naphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d Pyran-9,10-dibutyldicarboxylate) was obtained as a yellow-green solid in a yield of 70% and 71% ee. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.45 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 8.7 Hz, 2H), 7.20 (d, J = 8. 1 Hz, 2H), 6.81 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H), 6.58 (ddd, J = 8.4, 6.9, and 1.2 Hz, 2H) 5.53 (d, J = 13.8 Hz, 2H), 4.89 (d, J = 13.8 Hz, 2H), 4.46 (dt, J = 10.8, and 6.6 Hz, 2H), 4.30 (dt, J = 10.8, and 6.6 Hz, 2H), 1.71-1.83 (m, 4H), 1.42-1.58 (m, 4H), 1.00 (t , 7.2Hz, 6H)

[Example 6]
Production of helicene derivative (6):
According to the following (1) and (2), the helicene derivative 8H, 11H-9,10-dibutylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [d] pyran was synthesized.

(1) Synthesis of triyne (di (2-hept-2-ynyloxynaphthalen-1-yl) acetylene):
Di (2-hept-2) represented by the formula (IV-6) was obtained in the same manner as in Example 3 (1) except that 1-bromo-2-heptin was used instead of 1-bromo-2-butyne. -Inyloxynaphthalen-1-yl) acetylene was obtained as a pale yellow solid in a yield of 50%. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 8.67 (d, J = 7.5 Hz, 2H), 7.79-7.85 (m, 4H), 7.60 (ddd, J = 8.1) 6.6, and 1.2 Hz, 2H), 7.40-7.46 (m, 4H), 5.04 (t, J = 2.1 Hz, 4H), 2.23 (tt, J = 6.9) , And 2.1 Hz, 4H), 1.28-1.53 (m, 8H), 0.85 (t, 7.2 Hz, 6H)

(2) Helicene (8H, 11H-9,10-dibutylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo -[D] pyran) synthesis:
In the same manner as in Example 1 (8) except that di (2-hept-2-ynyloxynaphthalen-1-yl) acetylene obtained in (1) is used as triyne, formula (II-6) 8H, 11H-9,10-dibutylnaphtho [2,1-b] naphtha [1 ″, 2 ″: 5 ′, 6 ′] pyrano [3 ′, 4 ′: 5,6] benzo- [ d] Pyran was obtained as a pale yellow solid in 50% yield. ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ , 300 MHz) δ 7.40 (d, J = 8.7 Hz, 2H), 7.26 (d, J = 8.7 Hz, 2H), 7.19 (d, J = 8. 1 Hz, 2H), 6.91 (d, J = 8.1 Hz, 2H), 6.76 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H), 6.52 (ddd, J = 8.1, 6.9, and 1.2 Hz, 2H), 5.52 (d, J = 12.6 Hz, 2H), 4.71 (d, J = 12.6 Hz, 2H), 2.77 ( t, J = 7.5 Hz, 4H), 1.46-1.71 (m, 8H), 1.04 (t, 6.9 Hz, 6H)

  In addition to being used as a material for molecular recognition, the present invention is expected to be applied to various optical devices such as organic EL elements, fluorescent materials, organic buffer layer constituent materials, and nonlinear optical materials [7] helicene derivatives, It can be advantageously used as a method for producing the [7] helicene derivative and a triyne derivative serving as an intermediate.

Claims (7)

A helicene derivative represented by the following formula (I):

(In formula (I), at least one of X ¹ and Y ¹ , X ² and Y ² is present, respectively, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.) It is represented by following formula (II), The helicene derivative of Claim 1 characterized by the above-mentioned.

(In formula (II), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.) The E ¹ and / or E ² are each independently one selected from the group consisting of a hydrogen atom, an alkyl group, an alkyl ether group, an alkyl ester group, and an alkyl ketone group. The helicene derivative according to claim 2. A triyne derivative represented by the following formula (III):

(In formula (III), at least one of X ¹ and Y ¹ , X ² and Y ² is present, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.) The triyne derivative according to claim 4, which is represented by the following formula (IV):

(In Formula (IV), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.) A method for producing a helicene derivative, wherein a triyne derivative represented by the following formula (III) is cyclized and trimerized using a rhodium compound represented by the following formula (X).

(In formula (X), L represents a bisphosphine represented by R ¹ R ² PQ-PR ³ R ⁴ , Y represents a non-conjugated diene compound, X represents BF ₄ , PF ₆ , BPh ₄ , Represents ClO ₄ , SbF ₆ or CF ₃ SO ₃ , m represents 1 or 2, n represents 0 or 1, provided that when m = 1, n represents 0 or 1 and m = 2 In this case, n represents 0. R ¹ , R ² , R ³ and R ⁴ each independently represents an aryl group which may have a substituent or a cycloalkyl group which may have a substituent. Q represents a divalent arylene group which may have a substituent.

(In formula (III), at least one of X ¹ and Y ¹ , X ² and Y ² is present, and X ¹ , X ² , Y ¹ and Y ² are each independently CH ₂ , C = O, O, N, S, P, B, or Si, and N, S, P, B, or Si may be bonded to any one of CH ₂ , C═O, and O. E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group, heterocyclic group or Indicates any of these derivatives.) The method for producing a helicene derivative according to claim 6, wherein the triyne derivative is represented by the following formula (IV).

(In Formula (IV), E ¹ and E ² are each independently a hydrogen atom, alkyl group, aryl group, allyl group, benzyl group, alkenyl group, alkynyl group, alkyl ether group, alkyl ester group, alkyl ketone group. Represents a heterocyclic group or a derivative thereof.)