JP7367927B2 - Compounds having allyl ether and allylsilane skeletons and methods for producing the same - Google Patents

Description

The present invention relates to compounds having allyl ether and allylsilane skeletons and methods for producing the same.

一方、本発明者らは、酸化的カップリングによりアリル位にシリル基を導入する方法を開発してきた（非特許文献３参照。）。また、パラジウム錯体及び／又はパラジウム塩並びに酸素ガスの存在下、１，３－ジエンと２級アミンとジシランを反応させることで、アリルアミンおよびアリルシラン骨格を有する化合物を簡便に合成することができる方法を開発してきた（特許文献１参照。）。 Compounds having an allyl ether or allylsilane skeleton are used as pharmaceuticals, natural compounds, and important intermediates in the synthesis of these compounds. For example, compounds having an allyl ether skeleton include isoleucine antagonists and anti-HIV compounds. Allylsilane is used in the total synthesis of metabolic products of marine organisms. Therefore, compounds having allyl ether and allylsilane skeletons in the same molecule are considered to have a wide range of applications. As a method for synthesizing such a compound, 3-benzyl-1-propene is synthesized by the method described in Non-Patent Document 1, and 3-benzyl-1-propene is synthesized using a first generation Grubbs catalyst having two phosphine ligands. A method of subjecting 1-propene and 3-trimethylsilyl-1-propene to a metathesis reaction has been reported (see Non-Patent Document 2). Non-Patent Document 2 examines the selectivity of olefin cross metathesis (CM), and converts 1,4-butanediol and 1,3-dibromopropene into allyl ether and allylsilane skeletons within the same molecule using a Grignard reagent. It has also been reported that a compound having the following is synthesized (see Non-Patent Document 2). This reaction requires multiple synthetic steps, requires the use of halogen as a substrate, and produces an equivalent amount of salt as a by-product.

On the other hand, the present inventors have developed a method for introducing a silyl group into an allyl position by oxidative coupling (see Non-Patent Document 3). In addition, we have developed a method for easily synthesizing compounds having allylamine and allylsilane skeletons by reacting 1,3-diene, secondary amine, and disilane in the presence of a palladium complex and/or palladium salt and oxygen gas. (See Patent Document 1.)

JP2017-088507A

P. V. Pham, K. Ashton and David W. C. MacMillan, Chem. Sci., 2011, 2, 1470. A. K. Chatterjee, T.-L. Choi, D. P. Sanders, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 11360. S. Nakai, M. Matsui, Y. Shimizu, Y. Adachi, Y. Obora, J. Org. Chem., 2015, 80, 7317.

According to the study by the present inventors, the method of introducing a silyl group at the allyl position by oxidative coupling disclosed in Non-Patent Document 3 is effective for It was found that this method cannot be applied to compounds with
In addition, the method reported in Non-Patent Document 2 produces compounds having allyl ether and allylsilane skeletons, but the reaction is difficult to proceed in the synthesis of polysubstituted alkenes, substrates are limited, and multi-stage synthesis steps are required. However, there are problems such as generation of halogen salts as by-products.
In view of the above, an object of the present invention is to provide a method for producing organic compounds having allyl ether and allylsilane skeletons under simple and mild conditions.

上記式中、Ｒ^１は、炭素数２～３０の置換若しくは無置換の炭化水素基を表し、Ｒ^２は、それぞれ独立して、水素原子又は炭素数１～２０の置換若しくは無置換の炭化水素基を表し、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。但し、２つのＲ^２が共に炭化水素基である場合、２つの炭化水素基が連結して環状構造を形成していてもよい。
［３］ 前記銅塩が、二価の銅の塩である、［１］又は［２］に記載のアリルエーテル及びアリルシラン骨格を有する化合物の製造方法。
［４］ 前記二官能基化反応工程において、１，４－ベンゾキノンを用いる、［１］～［３］のいずれかに記載のアリルエーテル及びアリルシラン骨格を有する化合物の製造方法。
［５］ 前記パラジウム錯体が、ビス（ジベンジリデンアセトン）パラジウム（０）である、［１］～［４］のいずれかに記載のアリルエーテル及びアリルシラン骨格を有する化合物の製造方法。
［６］ 式（Ｄ’）で表されるアリルエーテル及びアリルシラン骨格を有する化合物。

上記式中、Ｒ^１は、炭素数２～３０の置換若しくは無置換の炭化水素基を表し、Ｒ^２は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基を表し、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。但し、２つのＲ^２が連結して環状構造を形成していてもよい。 As a result of intensive studies to solve the above problems, the present inventors discovered that silicone (Si-O-Si) is usually formed when alcohol and disilane are reacted as substrates, but palladium complex and/or Alternatively, by reacting 1,3-diene, alcohol, and disilane in an oxygen atmosphere in the presence of a palladium salt and a copper salt, an oxygen atom is formed at a position distant from the silicon substituent rather than forming Si-O. They found a method to introduce this and succeeded in synthesizing a new organosilicon compound having an oxygen substituent, thereby completing the present invention.
The present invention provides the following specific aspects.
[1] Having an allyl ether and allylsilane skeleton, which includes a bifunctionalization reaction step in which 1,3-diene, alcohol, and disilane are reacted in an oxygen atmosphere in the presence of a palladium complex and/or palladium salt and copper salt. Method of manufacturing the compound.
[2] The alcohol is represented by formula (A), the 1,3-diene is represented by formula (B), the disilane is represented by formula (C), and the compound having the allyl ether and allylsilane skeleton is A method for producing a compound having an allyl ether and an allylsilane skeleton according to [1], which is represented by formula (D).

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms, and R ² each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a group, and each R 3 is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted group having 1 to 20 carbon atoms. or represents an unsubstituted acyl group. However, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure.
[3] The method for producing a compound having an allyl ether and allylsilane skeleton according to [1] or [2], wherein the copper salt is a divalent copper salt.
[4] The method for producing a compound having an allyl ether and allylsilane skeleton according to any one of [1] to [3], wherein 1,4-benzoquinone is used in the difunctionalization reaction step.
[5] The method for producing a compound having an allyl ether and allylsilane skeleton according to any one of [1] to [4], wherein the palladium complex is bis(dibenzylideneacetone)palladium(0).
[6] A compound having an allyl ether and allylsilane skeleton represented by formula (D').

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms, and R ² each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. , R ³ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted group having 1 to 20 carbon atoms represents an acyl group. However, two R ² may be connected to form a cyclic structure.

According to the present invention, compounds having allyl ether and allylsilane skeletons, which have been difficult to synthesize so far, can be produced easily and under mild conditions. Furthermore, according to the present invention, it is possible to synthesize tetrasubstituted alkenes, which has been difficult with conventional metathesis reactions.

In explaining the details of the present invention, specific examples will be given. However, the present invention is not limited to the following content as long as it does not depart from the spirit of the present invention, and the present invention can be implemented with appropriate changes.

1. Method for producing a compound having an allyl ether and an allylsilane skeleton A method for producing a compound having an allyl ether and an allylsilane skeleton according to an embodiment of the present invention includes a method for manufacturing a compound having an allyl ether and an allylsilane skeleton in the presence of a palladium complex and/or a palladium salt and a copper salt. It is characterized by including a difunctional grouping reaction step (hereinafter sometimes abbreviated as "reaction step") in which a diene, alcohol, and disilane are reacted in an oxygen atmosphere. Specifically, for example, the following reactions may be mentioned. Note that "compounds having allyl ether and allylsilane skeletons" refer to allyl ether skeletons (-O-C-C=C-) and allylsilane skeletons (-C=C-C-Si) that share an allyl group. It means an organic compound containing the compound, and other structures are not particularly limited.

In general, disilane and alcohol have a high affinity, so when alcohol and disilane are used in a reaction, silicone (Si-O-Si) is usually formed and a silyl ether is formed. The present inventors discovered that 1,3-diene, in the presence of a palladium complex and/or a palladium salt and a copper salt,
It was discovered that when disilane and alcohol are reacted in an oxygen atmosphere where the transition metal catalyst is deactivated, the alcohol can be used as an alkoxylating agent. We came up with a method of introducing oxygen atoms and succeeded in synthesizing a new organosilicon compound with an oxygen substituent. The method for producing compounds having allyl ether and allylsilane skeletons according to an embodiment of the present invention can perform the addition of alcohol and disilane to 1,3-diene in one step under relatively mild conditions, and can perform the addition of alcohol and disilane to 1,3-diene in one step. Compared to conventional methods that require step-by-step reactions, compounds having both allyl ether and allylsilyl skeletons can be produced very efficiently. In addition, since silylation is performed using disilane, it can be said to be superior from a safety perspective compared to the case where halogenated silanes are used, and it can be said to be an environmentally friendly material conversion technology. Furthermore, this reaction allows the synthesis of tetrasubstituted alkenes, which is difficult to achieve using conventional metathesis reactions.

In one embodiment of the present invention, an alcohol represented by formula (A), a 1,3-diene represented by formula (B), and a formula ( It is preferable to include a difunctionalization reaction step in which the disilane represented by C) is reacted in an oxygen atmosphere.

上記式中、Ｒ^１は、炭素数２～３０の置換若しくは無置換の炭化水素基を表し、Ｒ^２は、それぞれ独立して、水素原子又は炭素数１～２０の置換若しくは無置換の炭化水素基を表し、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。但し、２つのＲ^２が共に炭化水素基である場合、２つの炭化水素基が連結して環状構造を形成していてもよい。
以下、「アルコール」、「１，３－ジエン」、「ジシラン」、「パラジウム錯体」、「パラジウム塩」等について詳細に説明する。

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms, and R ² each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a group, and each R 3 is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted group having 1 to 20 carbon atoms. or represents an unsubstituted acyl group. However, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure.
Hereinafter, "alcohol", "1,3-diene", "disilane", "palladium complex", "palladium salt", etc. will be explained in detail.

(alcohol)
The specific type of alcohol used in the present invention is not particularly limited, and should be appropriately selected depending on the compound having an allyl ether and allylsilane skeleton to be produced. Preferably, alcohol represented by formula (A) (hereinafter sometimes abbreviated as "alcohol") is used.
R ¹ -OH (A)
In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms. As used herein, the term "hydrocarbon group" is not limited to a linear saturated hydrocarbon group, but also means that it may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. .
The number of carbon atoms in R ¹ is usually 30 or less, preferably 24 or less, and more preferably 20 or less.
Examples of the unsubstituted hydrocarbon group having 2 to 30 carbon atoms represented by R ¹ include ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert -Butyl group, n-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group alkyl groups such as n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-docosyl group; cyclopropyl group, Cycloalkyl groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group aromatic hydrocarbon groups such as 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-triphenylenyl group, 2-triphenylenyl group; etc. can be mentioned.
When the hydrocarbon group represented by R ¹ has a substituent, the substituent includes a deuterium atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Alkyl groups having 1 to 4 carbon atoms such as isobutyl group and tert-butyl group; cycloalkyl groups having 3 to 4 carbon atoms such as cyclopropyl group and cyclobutyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, etc. Aromatic hydrocarbon groups having 6 to 10 carbon atoms; heterocyclic groups such as oxygen-containing heterocyclic groups such as furanyl groups, sulfur-containing heterocyclic groups such as thienyl groups, nitrogen-containing heterocyclic groups such as pyrrolyl groups and pyridyl groups; etc. can be mentioned. Therefore, when the hydrocarbon group represented by R ¹ has a substituent, examples of R ¹ include an aralkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group; a cyclohexylmethyl group; cycloalkylalkyl groups such as; hydrocarbon groups having an oxygen-containing heterocycle such as furfuryl group; hydrocarbon groups having a sulfur-containing heterocycle such as thienylmethyl group; hydrocarbon groups having a nitrogen-containing heterocycle such as pyridylmethyl group Preferred examples include benzyl group and 1-naphthylmethyl group.
Note that when the hydrocarbon group having 2 to 30 carbon atoms has a substituent, the number of carbon atoms means the total number of carbon atoms of the substituent and the number of carbon atoms of the hydrocarbon group.
Examples of the alcohol include those represented by the following formula.

上記式中、Ｒ^２は、それぞれ独立して、水素原子又は炭素数１～２０の置換若しくは無置換の炭化水素基を表す。但し、２つのＲ^２が共に炭化水素基である場合、２つの炭化水素基が連結して環状構造を形成していてもよい。
Ｒ^２が炭化水素基である場合の炭素数は、通常２０以下、好ましくは１５以下、より好ましくは１２以下である。
Ｒ^２で表される炭素数１～２０の無置換の炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｉｓｏ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウ
ンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、ｎ－ドコシル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、１－ナフチル基、２－ナフチル基、１－ナフチル基、２－ナフチル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、４－フェナントリル基、９－フェナントリル基、１－アントリル基、２－アントリル基、９－アントリル基、１－ピレニル基、２－ピレニル基、４－ピレニル基、１－トリフェニレニル基、２－トリフェニレニル基等の芳香族炭化水素基；等が挙げられる。
Ｒ^２で表される炭化水素基が置換基を有する場合、前記置換基としては、重水素原子；メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等の炭素数１～４のアルキル基；シクロプロピル基、シクロブチル基等の炭素数３～４のシクロアルキル基；フェニル基、１－ナフチル基、２－ナフチル基等の炭素数６～１０の芳香族炭化水素基；等が挙げられる。
なお、前記炭素数１～２０の炭化水素基が置換基を有する場合、前記炭素数は、置換基の炭素数と炭化水素基の炭素数との合計の炭素数を意味する。また、２つのＲ^２が共に炭化水素基である場合、２つの炭化水素基が連結して環状構造を形成していてもよいが、その環状構造の炭素数は２０以下となるものとする。 (1,3-diene)
The specific type of 1,3-diene used in the present invention is not particularly limited, and should be appropriately selected depending on the compound having an allyl ether and allylsilane skeleton to be produced. Preferably, 1,3-diene (hereinafter sometimes abbreviated as "diene") represented by formula (B) is used.

In the above formula, R ² each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. However, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure.
When R ² is a hydrocarbon group, the number of carbon atoms is usually 20 or less, preferably 15 or less, and more preferably 12 or less.
Examples of the unsubstituted hydrocarbon group having 1 to 20 carbon atoms represented by R ² include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, and iso-butyl group. group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Alkyl groups such as n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-docosyl group; cyclo Cycloalkyl groups such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-naphthyl group, 2-naphthyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-triphenylenyl group, Aromatic hydrocarbon groups such as 2-triphenylenyl groups; and the like.
When the hydrocarbon group represented by R ² has a substituent, the substituent includes a deuterium atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Alkyl groups having 1 to 4 carbon atoms such as isobutyl group and tert-butyl group; cycloalkyl groups having 3 to 4 carbon atoms such as cyclopropyl group and cyclobutyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, etc. Examples include aromatic hydrocarbon groups having 6 to 10 carbon atoms; and the like.
Note that when the hydrocarbon group having 1 to 20 carbon atoms has a substituent, the number of carbon atoms means the total number of carbon atoms of the substituent and the number of carbon atoms of the hydrocarbon group. Further, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure, but the number of carbon atoms in the cyclic structure shall be 20 or less.

Examples of the 1,3-diene include those represented by the following formula.

The amount of diene used (charged amount) is usually 0.1 times or more, and usually 20 times or less, preferably 10 times or less, more preferably 5 times or less, and even more preferably 4 times or more, based on the amount of alcohol. It is less than twice that. Within the above range, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

式（Ｃ）中、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。
Ｒ^３の炭化水素基の炭素数は、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。
Ｒ^３で表される炭素数１～２０の無置換の炭化水素基としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｉｓｏ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ｉｓｏ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基、ｎ－ヘプタデシル基、ｎ－オクタデシル基、ｎ－ノナデシル基、ｎ－ドコシル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、１－ナフチル基、２－ナフチル基、１－フェナントリル基、２－フェナントリル基、３－フェナントリル基、４－フェナントリル基、９－フェナントリル基、１－アントリル基、２－アントリル基、９－アントリル基、１－ピレニル基、２－ピレニル基、４－ピレニル基、１－トリフェニレニル基、２－トリフェニレニル基等の芳香族炭化水素基；等が挙げられる。
Ｒ^３のアルコキシ基の炭素数は、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。
Ｒ^３で表される炭素数１～２０の無置換のアルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｉｓｏ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ペントキシ基、ｉｓｏ－ペントキシ基、ネオペントキシ基、ｎ－ヘキソキシ基、ｎ－ヘプトキシ基、ｎ－オクトキシ基等が挙げられる。
Ｒ^３のアシル基の炭素数は、通常２０以下、好ましくは１５以下、より好ましくは１０以下である。
Ｒ^３で表される炭素数１～２０の無置換のアシル基としては、アセチル基、プロピオニル基、ｎ－ブタノイル基、ｓｅｃ－ブタノイル基、ｎ－ペンタノイル基、ピバロイル基、フェニルアセチル基、シクロヘキシルカルボニル基、ベンゾイル基、ナフトイル基等が挙げられる。
Ｒ^３で表される炭化水素基、アルコキシ基又はアシル基が置換基を有する場合、前記置換基としては、重水素原子；フッ素原子；メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等の炭素数１～４のアルキル基；シクロプロピル基、シクロブチル基等の炭素数３～４のシクロアルキル基；フェニル基、１－ナフチル基、２－ナフチル基等の炭素数６～１０の芳香族炭化水素基；メトキシ基、エトキシ基、ブトキシ基等のアルコキシ基；アセチル基、ピバロイル基、ベンゾイル基等のアシル基；等が挙げられる。
なお、前記炭素数１～２０の炭化水素基、アルコキシ基、又はアシル基が置換基を有する場合、前記炭素数は、置換基の炭素数と炭化水素基、アルコキシ基、又はアシル基の炭素数との合計の炭素数を意味する。Ｒ^３は、炭化水素基を含むことが好ましく、ジシランの２つのケイ素原子に結合する３つのＲ^３の内、２つ以上が炭化水素基であることが好ましい。
ジシランとしては、下記式で表されるものが好ましく挙げられる。

(Disilane represented by formula (C))
The specific type of disilane used in the present invention is not particularly limited, and should be appropriately selected depending on the compound having an allyl ether and allylsilane skeleton to be produced. Preferably, disilane represented by formula (C) (hereinafter sometimes abbreviated as "disilane") is used.

In formula (C), R ³ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. represents a substituted or unsubstituted acyl group.
The number of carbon atoms in the hydrocarbon group of R ³ is usually 20 or less, preferably 15 or less, and more preferably 10 or less.
Examples of the unsubstituted hydrocarbon group having 1 to 20 carbon atoms represented by R ³ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group. group, tert-butyl group, n-pentyl group, iso-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Alkyl groups such as n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-docosyl group; cyclo Cycloalkyl groups such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; phenyl group, 1-naphthyl group, 2-naphthyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, Aromatic hydrocarbons such as 9-phenanthryl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 1-triphenylenyl group, 2-triphenylenyl group group; etc.
The number of carbon atoms in the alkoxy group of R ³ is usually 20 or less, preferably 15 or less, and more preferably 10 or less.
The unsubstituted alkoxy group having 1 to 20 carbon atoms represented by R ³ includes methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, iso-butoxy group , tert-butoxy group, n-pentoxy group, iso-pentoxy group, neopentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group and the like.
The number of carbon atoms in the acyl group of R ³ is usually 20 or less, preferably 15 or less, and more preferably 10 or less.
Examples of the unsubstituted acyl group having 1 to 20 carbon atoms represented by R ³ include acetyl group, propionyl group, n-butanoyl group, sec-butanoyl group, n-pentanoyl group, pivaloyl group, phenylacetyl group, cyclohexylcarbonyl group. group, benzoyl group, naphthoyl group, etc.
When the hydrocarbon group, alkoxy group or acyl group represented by R ³ has a substituent, the substituent includes a deuterium atom; a fluorine atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-propyl group; -Alkyl groups having 1 to 4 carbon atoms such as butyl group, sec-butyl group, isobutyl group, and tert-butyl group; cycloalkyl groups having 3 to 4 carbon atoms such as cyclopropyl group and cyclobutyl group; phenyl group, 1- Aromatic hydrocarbon groups having 6 to 10 carbon atoms such as naphthyl group and 2-naphthyl group; alkoxy groups such as methoxy group, ethoxy group and butoxy group; acyl groups such as acetyl group, pivaloyl group and benzoyl group; It will be done.
In addition, when the hydrocarbon group, alkoxy group, or acyl group having 1 to 20 carbon atoms has a substituent, the number of carbon atoms is the number of carbon atoms of the substituent and the number of carbon atoms of the hydrocarbon group, alkoxy group, or acyl group. means the total number of carbon atoms. R ³ preferably contains a hydrocarbon group, and preferably two or more of the three R ³ bonded to the two silicon atoms of disilane are hydrocarbon groups.
As the disilane, those represented by the following formula are preferably mentioned.

The amount of disilane to be used (the amount charged) is usually 0.1 times or more and usually 20 times or less, preferably 10 times or less, more preferably 5 times or less, and even more preferably 4 times or more, based on the amount of alcohol. It is less than twice that. Within the above range, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

(Palladium complex/palladium salt)
In the reaction process, the palladium complex and/or palladium salt acts as a catalyst. The oxidation number of palladium, specific types of ligands or counterions, etc. in palladium complexes and palladium salts (hereinafter sometimes abbreviated as "palladium complexes, etc.") are not particularly limited, and are appropriately selected depending on the purpose. be able to.
The oxidation number of palladium is usually 0, +1, +2, +4, or +6, but preferably +2.
Ligands or counterions, or compounds that can serve as these, include acetic acid, 2,4,6-trimethylbenzoic acid (TMBA), trifluoroacetic acid (TFA), benzonitrile (PhCN), and dibenzylideneacetone (dba). , acetylacetone (acac), chloride anion (Cl ⁻ ), bromide anion (Br ⁻ ), and the like.
In addition, in the reaction process, in addition to directly charging the palladium complex etc. into the reactor, a precursor containing the palladium element and a compound that can be a ligand or counter ion are added as additives to form the desired palladium complex in the reactor. etc. may be formed. For example, forming palladium (II) 2,4,6-trimethylbenzoate (Pd(TMBA) ₂ ) by reacting palladium (II) acetate with 2,4,6-trimethylbenzoic acid (TMBA). can be mentioned.
Examples of precursors containing palladium element include palladium(II) chloride (PdCl ₂ ), palladium(II) bromide (PdBr ₂ ), palladium(II) acetate (Pd(CH ₃ CO ₂ ) ₂ ), and trichloride. Examples include palladium(II) fluoroacetate (Pd(CF ₃ CO ₂ ) ₂ ).
Examples of palladium complexes include palladium(II) acetate (Pd(OAc) ₂ ), palladium(II) 2,4,6-trimethylbenzoate (Pd(TMBA) ₂ ), palladium(II) trifluoroacetate (Pd( TFA) ₂ ), bis(benzonitrile)dichloropalladium(II) ( _PdCl2 (PhCN) ₂ ), bis(dibenzylideneacetone)palladium(
0) (Pd(dba) ₂ ), acetylacetone palladium (II) (Pd(acac) ₂ ), and the like. With the above, compounds having allyl ether and allylsilane skeletons can be produced more efficiently. Among these, bis(dibenzylideneacetone)palladium(0) (Pd(dba) ₂ ) is preferred.

The amount of palladium complex etc. to be used (prepared amount) is usually 0.0001 times or more, preferably 0.001 times or more, more preferably 0.01 times or more, and usually 1 times the amount of alcohol. It is preferably 0.5 times or less, more preferably 0.2 times or less. Within the above range, compounds having allyl ether and allylsilane skeletons can be produced more efficiently. One type of palladium complex or the like may be used, or two or more types may be used.

(copper salt)
The copper salt used in the reaction step is not particularly limited, and examples thereof include CuI, CuCl, _CuCl2 , CuBr, _CuBr2 , _CuSO4 , Cu( _NO3 ) ₂ , Cu( _BF4 ) _2, and the like. Among these, copper halides are preferred, and divalent copper salts such as CuCl ₂ and CuBr ₂ are more preferred. One type of copper salt may be used, or two or more types may be used.

The amount of copper salt used (prepared amount) is usually 0.0001 times or more, preferably 0.001 times or more, more preferably 0.01 times or more, and usually 1 time or less relative to the alcohol. , preferably 0.5 times or less, more preferably 0.2 times or less. Within the above range, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

(oxygen gas)
Although the reaction step is characterized in that it is carried out under an oxygen atmosphere, a gas other than oxygen gas such as an inert gas may be present within a range that does not impair the effects of the present invention. Further, the reaction step may be carried out under either pressurized or reduced pressure conditions, usually at least 0.01 atm, preferably at least 0.05 atm, more preferably at least 0.1 atm, and usually at most 10 atm, preferably is 5 atm or less, more preferably 2 atm or less.

(solvent)
In the reaction step, it is usually preferable to use a solvent. In addition, the type of solvent is not particularly limited and can be selected as appropriate depending on the purpose; specifically, hydrocarbon solvents such as hexane, benzene, toluene, etc.; ether solvents such as diethyl ether, tetrahydrofuran (THF), etc. Solvent: Aprotic polar solvents such as dimethylacetamide (DMA), N,N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP) can be mentioned. Among these, N,N-dimethylformamide (DMF) is particularly preferred. One type of solvent may be used, or two or more types may be used.
With the above, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

(Additive)
In the reaction step, it is preferable to use an additive that can contribute to the reoxidation of copper or serves as a ligand for the Pd catalyst. Such additives include hydroquinone, 1,4-benzoquinone, methoxybenzoquinone, 2,5-di-tert-amylbenzoquinone, 2,3,5-trimethyl-1,4-benzoquinone, 2,5-dihydroxy- Quinones such as 1,4-benzoquinone, tetrahydroxy-1,4-benzoquinone, anthraquinone, 1,4-anthracenedione, 2-ethylanthraquinone naphthoquinone, 2,3-dichloro-5,6-dicyano-p-benzoquinone; Examples include metal salts such as silver salts, and from the viewpoint of improving yield, it is preferable to use 1,4-benzoquinone. One type of additive may be used, or two or more types may be used.
By using the above additives, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

(Reaction conditions)
The reaction temperature in the reaction step is usually 25°C or higher, preferably 40°C or higher, more preferably 60°C or higher, and usually 200°C or lower, preferably 150°C or lower, more preferably 100°C or lower.
The reaction time of the reaction step is usually 1 hour or more, preferably 3 hours or more, more preferably 6 hours or more, and usually 120 hours or less, preferably 96 hours or less, more preferably 72 hours or less.
Within the above range, compounds having allyl ether and allylsilane skeletons can be produced more efficiently.

(Other processes)
The method for producing a compound having an allyl ether and allylsilane skeleton according to the present embodiment may include any other steps in addition to the above bifunctionalization step. The optional step includes a purification step for increasing the purity of the allyl ether and allylsilane skeleton-containing compound. In the purification step, purification methods commonly used in the field of organic synthesis, such as filtration, adsorption, column chromatography, and distillation, can be employed.

上記式中、Ｒ^１は、炭素数２～３０の置換若しくは無置換の炭化水素基を表し、Ｒ^２は、それぞれ独立して、水素原子又は炭素数１～２０の置換若しくは無置換の炭化水素基を表し、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。但し、２つのＲ^２が共に炭化水素基である場合、２つの炭化水素基が連結して環状構造を形成していてもよい。 The compound having an allyl ether and an allylsilane skeleton produced by the manufacturing method according to the embodiment of the present invention described above is not particularly limited in its specific type as long as it has both an allyl ether and an allylsilane skeleton. It is preferable to use a compound that can produce a Z-form and has an allyl ether and an allylsilane skeleton represented by the following formula (D).

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms, and R ² each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. R ³ represents a group, and each R 3 is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted group having 1 to 20 carbon atoms. or represents an unsubstituted acyl group. However, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure.

上記式中、Ｒ^１は、炭素数２～３０の置換若しくは無置換の炭化水素基を表し、Ｒ^２は
、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基を表し、Ｒ^３は、それぞれ独立して、炭素数１～２０の置換若しくは無置換の炭化水素基、炭素数１～２０の置換若しくは無置換のアルコキシ基、又は炭素数１～２０の置換若しくは無置換のアシル基を表す。但し、２つのＲ^２が連結して環状構造を形成していてもよい。
なお、Ｒ^１、Ｒ^２、Ｒ^３については、項目「１．アリルエーテル及びアリルシラン骨格を有する化合物の製造方法」において説明したものと同義である。
アリルエーテルおよびアリルシラン骨格を有する化合物は、例えば、下記式に示されるように、さらなる反応への応用が可能である。本発明の一実施形態に係るアリルエーテルおよびアリルシラン骨格を有する化合物は、医薬品、工業的化成品などの各種用途への応用が期待される。 2. Compounds Having Allyl Ether and Allyl Silane Skeletons It has been mentioned above that compounds having allyl ether and allyl silane skeletons represented by formula (D) can be produced by the production method of the present invention. Compounds having allyl ether and allylsilane skeletons are also an embodiment of the present invention.

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 2 to 30 carbon atoms, and R ² each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. , R ³ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted group having 1 to 20 carbon atoms represents an acyl group. However, two R ² may be connected to form a cyclic structure.
Note that R ¹ , R ² , and R ³ have the same meanings as those explained in the item "1. Method for producing a compound having an allyl ether and an allylsilane skeleton."
Compounds having allyl ether and allylsilane skeletons can be applied to further reactions, for example, as shown in the following formula. The compound having an allyl ether and allylsilane skeleton according to an embodiment of the present invention is expected to be applied to various uses such as pharmaceuticals and industrial chemical products.

The present invention will be described in more detail with reference to Examples below, but changes can be made as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below.

(Examination of amount of substrate)
[Experiment example 1]
Pd(dba) ₂ (5 mol%, 0.0287 g) and CuI (10 mol%, 0.0190 g) were placed in a 30 mL eggplant flask equipped with a stirrer, and N,N-dimethylformamide (DMF) (3 mL) was added thereto. was added and the atmosphere was replaced with argon. Thereafter, the mixture was stirred at room temperature for 30 minutes. After stirring, hexamethyldisilane (3 mmol, 0.4 g), benzyl alcohol (1 mmol, 0.108 g), and 2,3-dimethyl-1,3-butadiene (3 mmol, 0.246 g) were added. Attach a two-way cock and a balloon containing oxygen gas to the top of the reflux tube to create an oxygen atmosphere in the system, heat it to 70°C (reaction temperature) in an oil bath, and keep stirring for 16 hours (reaction time). ) reacted. After the reaction was completed, toluene (10 mL) was added as a quenching solvent to wash the inside of the reflux tube.
The conversion rate of the substrate and the yield of the product, etc. are calculated using the internal standard method (internal standard substance: decane) (the results are shown in Table 1), and the product is analyzed by NMR, GC-MS, etc. Qualitative analysis was conducted. As a result, it was confirmed that a compound having an allyl ether and an allylsilane skeleton represented by the following formula 4 was produced. Moreover, the yield of the product was calculated based on benzyl alcohol.
The results of NMR measurement of the product are shown below.
¹ H-NMR (400MHz; CDCl ₃ ) δ: 7.38-7.37 (m, 5H), 7.30-7.27 (m, 5H), 4.49 (s, 2H), 3.94 (s, 2H), 1.78 (dd, J = 1.8, 0.9 Hz, 3H), 1.71 (dd, J = 1.7, 0.8 Hz, 3H), 1.62 (d, J = 0.9 Hz, 2H), 0.00 (s, 9H).
¹³ C-NMR (100MHz; CDCl ₃ ) δ: 139.77 (C), 132.82 (C), 129.20 (CH), 128.79 (CH), 128.35 (CH), 123.07 (C), 72.76 (CH ₂ ), 71.89 ( CH ₂ ), 26.48 (CH ₂ ), 22.60 (CH ₃ ), 17.54
(CH ₃ ), 0.00 (CH ₃ ).
GC-MS (EI) m/z (relative intensity) 262(1) [M] ⁺ , 73(100), 91(81), 82(73)
[Experiment Examples 2 and 3]
The reactions in Experimental Examples 2 and 3 were carried out in the same manner as in Experimental Example 1, except that the amount of 1,3-butadiene was changed as shown in Table 1. The results are shown in Table 1.

(Examination of amount of substrate)
[Experiment Examples 4 and 5]
The reaction was carried out in the same manner as in Experimental Example 2, except that the amount of 2,3-dimethyl-1,3-butadiene was changed as shown in Table 2. The results are shown in Table 2 together with the results of Experimental Example 2.

(Study of additives)
[Experiment Examples 6 to 8]
The reaction was carried out in the same manner as in Experimental Example 2, except that the type of additive was changed from copper iodide (CuI) as shown in Table 3. The results are shown in Table 3 together with the results of Experimental Example 2.

上記結果から、一価のヨウ化銅、臭化銅、塩化銅よりも、二価の塩化銅を用いた場合に、より収率が向上することがわかる。

From the above results, it can be seen that the yield is improved more when divalent copper chloride is used than monovalent copper iodide, copper bromide, or copper chloride.

(Study of Pd catalyst)
[Experiment example 9]
The reaction of Experimental Example 9 was carried out in the same manner as Experimental Example 6 except that the type of catalyst was changed from the palladium complex Pd(dba) ₂ as shown in Table 4. The results are shown in Table 4 together with the results of Experimental Example 6.

(Examination of amount of substrate)
[Experiment example 10]
The reaction of Experimental Example 22 was carried out in the same manner as Experimental Example 6 except that the amount of hexamethyldisilane was changed as shown in Table 5. The results are shown in Table 5 together with the results of Experimental Example 6.

実験例６と実験例１０とを比較すると、化合物４の収率にはほとんど変化はないが、基質のジシランが全て転化したことがわかる。

Comparing Experimental Example 6 and Experimental Example 10, it can be seen that although there is almost no change in the yield of Compound 4, all of the substrate disilane was converted.

(Study of additives)
[Experiment example 11]
The reaction of Experimental Example 11 was carried out in the same manner as Experimental Example 10, except that the types of additives were changed as shown in Table 6. The results are shown in Table 6 together with the results of Experimental Example 10.

実験例１０と１１とを比較すると、塩化銅より臭化銅のほうが収率が高いことがわかる。

Comparing Experimental Examples 10 and 11, it can be seen that the yield of copper bromide is higher than that of copper chloride.

(Study of additives)
[Experiment example 12]
Pd(dba) ₂ (5 mol%, 0.02
87 g), CuCl (10 mol%, 0.0099 g), and 1,4-benzoquinone (40 mol%, 0.0432 g) were added thereto, and N,N-dimethylformamide (DMF) (3 mL) was added thereto, and the atmosphere was replaced with argon. Thereafter, the eggplant flask was stirred at room temperature for 30 minutes using a stirrer. After stirring, hexamethyldisilane (4 mmol, 0.586 g), benzyl alcohol (1 mmol, 0.108 g), and 2,3-dimethyl-1,3-butadiene (3 mmol, 0.246 g) were added. Attach a two-way cock and a balloon containing oxygen gas to the top of the reflux tube to create an oxygen atmosphere in the system, heat it to 70°C (reaction temperature) in an oil bath, and keep stirring for 16 hours (reaction time). ) reacted. After the reaction was completed, toluene (10 mL) was added as a quenching solvent to wash the inside of the reflux tube.
The conversion rate of the substrate and the yield of the product, etc. are calculated using the internal standard method (internal standard substance: decane) (the results are shown in Table 7), and the product is analyzed by NMR, GC-MS, etc. Qualitative analysis was conducted. As a result, it was confirmed that a compound having an allyl ether and an allylsilane skeleton represented by the following formula 4 was produced. Moreover, the yield of the product was calculated based on benzyl alcohol.

[Experimental Examples 13 to 17]
The reaction was carried out in the same manner as in Experimental Example 12, except that the type of copper salt used as an additive was changed as shown in Table 7. The results are shown in Table 7.

上記の結果から、一価の銅塩より二価の銅塩を用いたほうが、高い収率が得られたことがわかる。特に、臭化銅(II)を用いた実験例１５は８８％もの収率を示した。

From the above results, it can be seen that a higher yield was obtained when a divalent copper salt was used than a monovalent copper salt. In particular, Experimental Example 15 using copper(II) bromide showed a yield of 88%.

(Examination of amount of substrate)
[Experimental Examples 18-21]
The reaction was carried out in the same manner as in Experimental Example 15, except that the amounts of 1,3-diene and disilane as substrates were changed as shown in Table 8. The results are shown in Table 8.

実験例１５、１８～２１から、アルコール：ジエン：ジシラン＝１：３：４の場合と、アルコール：ジエン：ジシラン＝１：５：４の場合で、顕著に高い収率を示した。転化率を考慮すると、実験例２１より実験例１５のアルコール：ジエン：ジシラン＝１：３：４での反応が特に好ましいことがわかる。

From Experimental Examples 15 and 18 to 21, significantly high yields were shown in the case of alcohol:diene:disilane=1:3:4 and in the case of alcohol:diene:disilane=1:5:4. Considering the conversion rate, it can be seen from Experimental Example 21 that the reaction in Experimental Example 15 using alcohol:diene:disilane=1:3:4 is particularly preferable.

(Examination of amount of additive)
[Experimental Examples 22 to 24]
The reactions in Experimental Examples 22 to 24 were carried out in the same manner as in Experimental Example 15, except that the amount of benzoquinone used was changed as shown in Table 9. The results are shown in Table 9 together with the results of Experimental Example 15.

実験例１５と２２～２４との比較から、ベンゾキノンを用いることで、収率が向上することがわかる。

A comparison of Experimental Examples 15 and 22 to 24 shows that the yield is improved by using benzoquinone.

(Consideration of atmosphere)
[Experimental Examples 25 and 26]
The reactions in Experimental Examples 25 and 26 were carried out in the same manner as in Experimental Example 15, except that the atmosphere was changed as shown in Table 10. The results are shown in Table 10 together with the results of Experimental Example 15.

実験例１５と実験例２５から、大気雰囲気下でも本反応が進行しないことがわかる。また、実験例２６との比較から、アルゴン雰囲気下でも本反応が進行しないことがわかる。

From Experimental Example 15 and Experimental Example 25, it can be seen that this reaction does not proceed even under atmospheric conditions. Furthermore, a comparison with Experimental Example 26 shows that this reaction does not proceed even under an argon atmosphere.

(Substrate consideration)
[Experiment Example 27]
The reaction of Experimental Example 27 was carried out in the same manner as Experimental Example 11 except that the type of alcohol was changed as shown in Table 11. The results are shown in Table 11 together with the results of Experimental Example 11.

１－ナフチルメタノールを基質として、アリルエーテルおよびアリルシラン骨格を有する四置換アルケンを１ステップで簡便に合成出来ることが示された。

It has been shown that tetrasubstituted alkenes having allyl ether and allylsilane skeletons can be easily synthesized in one step using 1-naphthylmethanol as a substrate.

According to the present invention, compounds having allyl ether and allylsilane skeletons, which have been difficult to synthesize so far, can be produced easily and under mild conditions. Furthermore, since the present invention does not require the use of halogen as a substrate, it can be said that the reaction is environmentally friendly and clean. Furthermore, according to the present invention, it is possible to synthesize tetrasubstituted alkenes, which has been difficult with conventional metathesis reactions, and novel compounds having an allylsilane skeleton that can be used for various applications such as pharmaceuticals and industrial chemical products are provided. .

Claims (4)

In the presence of a palladium complex and/or palladium salt and copper salt, a difunctionalization reaction step of reacting 1,3-diene, alcohol, and disilane in an oxygen atmosphere ,
The alcohol is represented by formula (A), the 1,3-diene is represented by formula (B), the disilane is represented by formula (C), and the compound having the allyl ether and allylsilane skeleton is represented by formula (D ) A method for producing a compound having an allyl ether and an allylsilane skeleton.

In the above formula, R ¹ represents a hydrocarbon group having 2 to 30 carbon atoms or a hydrocarbon group having 2 to 30 carbon atoms having a substituent, and the substituent is a deuterium atom or a hydrocarbon group having 1 to 4 carbon atoms. an alkyl group, a cycloalkyl group having 3 to 4 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; R 2 is each independently a hydrogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, or represents a hydrocarbon group having 1 to 20 carbon atoms and having a substituent, and the substituent is a deuterium atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or a cycloalkyl group having 6 to 4 carbon atoms. 10 aromatic hydrocarbon groups; R ³ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms having a substituent, or an alkoxy group having 1 to 20 carbon atoms; group, or an alkoxy group having 1 to 20 carbon atoms having a substituent, and the substituent is a deuterium atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, a carbon It is an aromatic hydrocarbon group of number 6 to 10 or an alkoxy group. However, when both R ² are hydrocarbon groups, the two hydrocarbon groups may be connected to form a cyclic structure. The method for producing a compound having allyl ether and allylsilane skeletons according to claim 1 , wherein the copper salt is a divalent copper salt. The method for producing a compound having an allyl ether and allylsilane skeleton according to claim 1 or 2 , wherein 1,4-benzoquinone is used in the difunctionalization reaction step. The method for producing a compound having an allyl ether and allylsilane skeleton according to any one of claims 1 to 3 , wherein the palladium complex is bis(dibenzylideneacetone)palladium(0).