JP2008195658A - Method for producing optically active cyclopropanecarboxylic esters rich in cis isomers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing optically active cyclopropanecarboxylic esters rich in cis isomers. <P>SOLUTION: The method for producing the optically active cyclopropanecarboxylic esters rich in cis isomers (e.g. optically active ethyl 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate rich in a cis isomer) comprises reacting diazoacetic esters (e.g. ethyl diazoacetate) with olefins (e.g. 1-acetoxy-3-methyl-2-butene) in the presence of an optically active rhodium compound (e.g. ämethyl tetrakis(2-oxopyrrolidine-5(S)-carboxylate)}dirhodium). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a process for producing cis-rich optically active cyclopropanecarboxylic acid esters.

（式中、Ｒ^４はアルキル基又はアリール基を表わす。Ｒ^５はアルキル基又はアリール基を表わす。＊は不斉炭素を表わす。）
で示される光学活性シクロプロパンカルボン酸エステル類には、−ＣＯ₂Ｒ^４で示される基と−ＣＨ₂ＯＣＯＲ^５で示される基とが、シクロプロパン環平面に対して、同じ側にあるシス体と反対側にあるトランス体とが存在し、シス体に富んだ式（４）で示される光学活性シクロプロパンカルボン酸エステル類は、医薬、農薬等の中間体として有用である（例えば、非特許文献１参照）。かかる式（４）で示されるシクロプロパンカルボン酸エステル類のシス体選択的不斉シクロプロパン化反応方法としては、例えば銅化合物と特定構造の光学活性なサリチルアルジミン類とを反応させて得られる不斉銅触媒の存在下に、式（２）

（式中、Ｒ^４はアルキル基又はアリール基を表わす。）
で示されるジアゾ酢酸エステル類と式（３）

（式中、Ｒ^５はアルキル基又はアリール基を表わす。）
で示されるオレフィン類を反応させることにより、シス体に富んだ式（４）で示される光学活性シクロプロパンカルボン酸エステル類が得られる方法（特許文献１）が知られているが、さらなるシス体比率の高い式（４）で示される光学活性シクロプロパンカルボン酸エステル類の製造方法が望まれている。
Ｔｅｔｒａｈｅｄｒｏｎ，５７，６０８３（２００１） 特開２００４−０５１４９９号公報 Formula (4)

(In the formula, R ⁴ represents an alkyl group or an aryl group. R ⁵ represents an alkyl group or an aryl group. * Represents an asymmetric carbon.)
In the optically active cyclopropanecarboxylic acid ester represented by the formula, a cis isomer in which the group represented by —CO ₂ R ⁴ and the group represented by —CH ₂ OCOR ⁵ are on the same side with respect to the plane of the cyclopropane ring An optically active cyclopropanecarboxylic acid ester represented by the formula (4) rich in cis isomer is useful as an intermediate for pharmaceuticals, agricultural chemicals and the like (for example, non-patented). Reference 1). As a cis-isomer-selective asymmetric cyclopropanation reaction method of the cyclopropanecarboxylic acid ester represented by the formula (4), for example, a reaction obtained by reacting a copper compound with an optically active salicylaldimine having a specific structure. In the presence of a homogeneous copper catalyst, the formula (2)

(In the formula, R ⁴ represents an alkyl group or an aryl group.)
And diazoacetic acid esters represented by the formula (3)

(In the formula, R ⁵ represents an alkyl group or an aryl group.)
There is known a method (Patent Document 1) in which an optically active cyclopropanecarboxylic acid ester represented by the formula (4) rich in cis isomer can be obtained by reacting the olefin represented by the formula (4). A method for producing optically active cyclopropanecarboxylic acid esters represented by the formula (4) having a high ratio is desired.
Tetrahedron, 57, 6083 (2001) JP 2004-051499 A

  Under such circumstances, the present inventor examined a method for producing cis-rich optically active cyclopropanecarboxylic acid esters, and in the presence of an optically active rhodium compound represented by the following formula (1). By reacting the diazoacetate represented by the formula (2) with the olefin represented by the formula (3), an optically active cyclopropanecarboxylic acid ester represented by the formula (4) rich in cis-isomer is obtained. The present invention has been found.

（式中、Ｒ¹は低級アルコキシカルボニル基、炭素数１〜６のアルキル基、アリール基又はアラルキル基を表わす。Ｒ^２及びＲ^３は、同一または相異なり、それぞれ水素原子、炭素数１〜６のアルキル基又はアリール基を表わす。Ｘは炭素又は酸素原子を表わす。＊は不斉炭素を表わす。）
で示される光学活性なロジウム化合物の存在下、式（２）

（式中、Ｒ^４はアルキル基又はアリール基を表わす。）
で示されるジアゾ酢酸エステル類と式（３）

（式中、Ｒ^５はアルキル基又はアリール基を表わす。）
で示されるオレフィン類を反応させることを特徴とする式（４）

（式中、Ｒ^４、Ｒ^５及び＊は上記と同一の意味を表わす。）
で示されるシス体リッチな光学活性シクロプロパンカルボン酸エステル類の製造方法を提供するものである。 That is, the present invention provides the formula (1)

(In the formula, R ¹ represents a lower alkoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group or an aralkyl group. R ² and R ³ are the same or different, and each represents a hydrogen atom or a carbon number of 1 to 6). And X represents a carbon or oxygen atom, and * represents an asymmetric carbon.)
In the presence of an optically active rhodium compound represented by formula (2)

(In the formula, R ⁴ represents an alkyl group or an aryl group.)
And diazoacetic acid esters represented by the formula (3)

(In the formula, R ⁵ represents an alkyl group or an aryl group.)
Formula (4) characterized by reacting olefins represented by formula (4)

(In the formula, R ⁴ , R ⁵ and * represent the same meaning as described above.)
A process for producing a cis-rich optically active cyclopropanecarboxylic acid ester represented by the formula:

According to the present invention, an optically active cyclopropanecarboxylic acid ester rich in cis form can be efficiently produced, which is industrially advantageous.

First, the optically active rhodium compound represented by formula (1) (hereinafter abbreviated as optically active rhodium compound (1)) will be described.
In the optically active rhodium compound represented by the formula (1), R ¹ represents, for example, a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl as the lower alkoxycarbonyl group. Group, isobutoxycarbonyl group, t-butoxycarbonyl group and the like.

  Examples of the lower alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, and cyclohexyl group. And linear or branched or cyclic alkyl groups. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include those composed of the above-described lower alkyl group and aryl group, such as a benzyl group and a trityl group.

In R ² and R ³ of formula (1), examples of the lower alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, a t-butyl group, Examples include linear or branched alkyl groups such as n-pentyl group, n-hexyl group, and cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group.

  Examples of such optically active rhodium compounds include {tetrakis (2-oxopyrrolidine-5 (S) -methyl carboxylate)} dirhodium, {tetrakis (2-oxopyrrolidine-5 (S) -ethyl carboxylate)} dirhodium. {Tetrakis (2-oxopyrrolidine-5 (S) -carboxylate n-propyl)} dirhodium, {Tetrakis (2-oxopyrrolidine-5 (S) -isopropyl carboxylate)} dirhodium, {Tetrakis (2-oxopyrrolidine) -5 (S) -carboxylate n-butyl)} dirhodium, {tetrakis (2-oxopyrrolidine-5 (S) -isobutylcarboxylate)} dirhodium, {tetrakis (2-oxopyrrolidine-5 (S) -carboxylic acid t-butyl)} rhodium,

{Tetrakis (4 (S) -methyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -methyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -methyl- 5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -methyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -methyl- 5,5-di-n-butyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -methyl-5,5-diphenyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -methyl- 5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -methyl-5,5-di (4- Tokishifeniru) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) - methyl-5,5-di (4-methylphenyl) -2-oxazolidinone)} dirhodium,

{Tetrakis (4 (S) -isopropyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -isopropyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -isopropyl- 5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isopropyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isopropyl- 5,5-di-n-butyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -isopropyl-5,5-diphenyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -isopropyl- 5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dirhodium, {teto Kiss (4 (S) -isopropyl-5,5-di (4-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isopropyl-5,5-di (4-methylphenyl)- 2-oxazolidinone)} rhodium,

{Tetrakis (4 (S) -isobutyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -isobutyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -isobutyl- 5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isobutyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isobutyl- 5,5-di-n-butyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isobutyl-5,5-diphenyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isobutyl- 5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dilodium, {tetrakis (4 (S -Isobutyl-5,5-di (4-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -isobutyl-5,5-di (4-methylphenyl) -2-oxazolidinone)} dirhodium ,

{Tetrakis (4 (S) -t-butyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -t-butyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S ) -T-butyl-5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -t-butyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -t-butyl-5,5-di-n-butyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -t-butyl-5,5-diphenyl-2-oxazolidinone)} Dirhodium, {tetrakis (4 (S) -t-butyl-5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S -T-butyl-5,5-di (4-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -t-butyl-5,5-di (4-methylphenyl) -2- Oxazolidinone)} rhodium,

{Tetrakis (4 (S) -phenyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -phenyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -phenyl- 5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -phenyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -phenyl- 5,5-di-n-butyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -phenyl-5,5-diphenyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -phenyl- 5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -phenyl- , 5-di (4-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) - phenyl-5,5-di (4-methylphenyl) -2-oxazolidinone)} dirhodium,

{Tetrakis (4 (S) -benzyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -benzyl-5,5-dimethyl-2-oxazolidinone)} dirhodium, {Tetrakis (4 (S) -benzyl- 5,5-diethyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -benzyl-5,5-di-n-propyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -benzyl- 5,5-di-n-butyl-2-oxazolidinone)} dilodium, {tetrakis (4 (S) -benzyl-5,5-diphenyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -benzyl- 5,5-di (2-methoxyphenyl) -2-oxazolidinone)} dilodium, {tetrakis (4 (S) -benzyl- , 5-di (4-methoxyphenyl) -2-oxazolidinone)} dirhodium, {tetrakis (4 (S) - benzyl-5,5-di (4-methylphenyl) -2-oxazolidinone)} dirhodium,
And the steric configuration (4S) at the 4-position of each compound was replaced by (4R), for example, {tetrakis (methyl 2-oxopyrrolidine-5 (R) -carboxylate)} dirhodium or {tetrakis (4 (R) -Methyl-2-oxazolidinone)} dirhodium and the like.

Specific examples of optically active rhodium compounds in which R ² and R ³ are different from each other include, for example, {tetrakis (4 (S) -methyl-5 (S) -phenyl-2-oxazolidinone)} dirhodium, {tetrakis (4 (S) -phenyl-5 (S) -phenyl-2-oxazolidinone)} dirhodium and the like.

  Such an optically active rhodium compound can be synthesized by a known method (J. Am. Chem. Soc. 115, 9968 (1993)).

In the diazoacetic acid esters represented by the formula (2) (hereinafter abbreviated as diazoacetic acid esters (2)), the alkyl group for R ⁴ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Examples thereof include a butyl group, an isobutyl group, a t-butyl group, and a 1-menthyl group. Examples of the aryl group include a phenyl group and a 2,6-di-t-butyl-4-methylphenyl group. Specific examples of the diazoacetic acid esters (2) include, for example, methyl diazoacetate, ethyl diazoacetate, n-propyl diazoacetate, isopropyl diazoacetate, n-butyl diazoacetate, isobutyl diazoacetate, tert-butyl diazoacetate, diazoacetic acid Menthyl, diazoacetic acid (2,6-di-t-butyl-4-methylphenyl) and the like. Such diazoacetic acid ester (2) can be prepared, for example, by reacting a corresponding amino acid ester with a diazotizing agent such as sodium nitrite.

In the olefins represented by formula (3) (hereinafter abbreviated as olefins (3)), R ⁵ represents an alkyl group or an aryl group. Examples of the alkyl group and aryl group are the same as those described in the description of the formula (2).

  Examples of the olefins (3) include 1-acetoxy-3-methyl-2-butene, 1-propionyloxy-3-methyl-2-butene, 1-butyryloxy-3-methyl-2-butene, and 1-isopropyl. Examples include carbonyloxy-3-methyl-2-butene, 1-benzoyloxy-3-methyl-2-butene, 1-tritylcarbonyloxy-3-methyl-2-butene and the like.

Such olefins (3) can be produced, for example, by reacting 3-methyl-2-buten-1-ol with a corresponding carboxylic acid halide in the presence of a base.

  The amount of the olefins (3) used is usually 1 mole or more with respect to the diazoacetic acid esters (2), and there is no particular upper limit. When the olefins (3) are liquid under the reaction conditions For this, a large excess amount of olefin (3) may be used as a solvent.

  The amount of the optically active rhodium compound (1) used is usually 0.01 to 10 mol% with respect to the diazoacetic acid esters (2).

  This reaction is usually carried out by contacting and mixing the optically active rhodium compound (1), diazoacetic acid ester (2) and olefin (3), and the mixing order is not particularly limited. The diazoacetic acid ester (2) may be added to the mixture with the copper complex and the olefin (3), or the olefin (3) and diazoacetic acid ester (2) may be added to the asymmetric copper complex. Good. The olefins (3) and diazoacetic acid esters (2) may be added continuously or intermittently. This reaction may be performed under normal pressure conditions or under pressurized conditions. The reaction temperature is generally −20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C.

    This reaction is usually carried out in the presence of a solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, and cyclohexane, aromatic hydrocarbon solvents such as toluene, and halogen such as dichloromethane and dichloroethane. Hydrocarbon solvents, for example, ester solvents such as ethyl acetate, etc. are used, and the amount used is not particularly limited. However, in view of economy, volume efficiency, etc., diazoacetate esters (2) are practically used. In contrast, it is 100 weight times or less. Further, as described above, when the olefin (3) is a liquid under the reaction conditions, the olefin (3) may be used as a solvent.

  After completion of the reaction, the insoluble matter is removed by filtration, if necessary, and then subjected to usual post-treatment such as distillation, column chromatography, etc., to thereby give an optically active cyclopropanecarboxylic acid represented by the cis-isomer rich formula (4). Acid esters are obtained.

  Examples of the optically active cyclopropanecarboxylic acid represented by the formula (4) include optically active methyl 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3-propionyloxymethyl-2,2-dimethylcyclohexane. Methyl propanecarboxylate, optically active methyl 3-n-propylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active methyl 3-isopropylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3 -Methyl benzylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active methyl 3-tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3-benzoyloxymethyl-2,2-dimethyl Black propanoic acid methyl,

Optically active ethyl 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active ethyl 3-propionyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3-butyryloxymethyl-2,2- Ethyl dimethylcyclopropanecarboxylate, optically active 3-isopropylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3-benzylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3 -Ethyl tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, ethyl optically active 3-benzoyloxymethyl-2,2-dimethylcyclopropanecarboxylate,

Optically active 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylic acid isopropyl, optically active 3-propionyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid isopropyl, optically active 3-butyryloxymethyl-2,2- Isopropyl dimethylcyclopropanecarboxylate, optically active 3-isopropylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate isopropyl, optically active 3-benzylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active 3 -Isopropyl tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active isopropyl 3-benzoyloxymethyl-2,2-dimethylcyclopropanecarboxylate,

Optically active 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate tert-butyl, optically active 3-propionyloxymethyl-2,2-dimethylcyclopropanecarboxylate tert-butyl, optically active 3-butyryloxymethyl- 2,2-dimethylcyclopropanecarboxylic acid tert-butyl, optically active 3-isopropylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid-tert-butyl, optically active 3-benzylcarbonyloxymethyl-2,2-dimethyl Tert-butyl cyclopropanecarboxylate, optically active 3-tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid tert-butyl, optically active 3-benzoyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid t rt- butyl,

Optically active 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylate menthyl, optically active 3-propionyloxymethyl-2,2-dimethylcyclopropanecarboxylate menthyl, optically active 3-butyryloxymethyl-2,2- Menthyl dimethylcyclopropanecarboxylate, optically active 3-isopropylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate menthyl, optically active 3-benzylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate menthyl, optically active 3 -Menthyl tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylate, optically active menthyl 3-benzoyloxymethyl-2,2-dimethylcyclopropanecarboxylate,

Optically active 3-acetoxymethyl-2,2-dimethylcyclopropanecarboxylic acid (2,6-di-t-butyl), optically active 3-propionyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid (2,6- Di-t-butyl), optically active 3-butyryloxymethyl-2,2-dimethylcyclopropanecarboxylic acid (2,6-di-t-butyl), optically active 3-isopropylcarbonyloxymethyl-2,2- Dimethylcyclopropanecarboxylic acid (2,6-di-t-butyl), optically active 3-benzylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid (2,6-di-t-butyl), optically active 3 -Tritylcarbonyloxymethyl-2,2-dimethylcyclopropanecarboxylic acid (2,6-di-t-butyl), optically active 3-benzoy Oxy-2,2-dimethylcyclopropane carboxylic acid (2,6-di -t- butyl), and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following examples, the cis form means that the acetoxymethyl group and the carboethoxy group are on the same side with respect to the cyclopropane ring plane, and the trans form means the cyclopropane ring plane. Means an acetoxymethyl group and a carboethoxy group on the opposite side. The yield was calculated by gas chromatography analysis, the cis / trans ratio, and the optical purity was calculated by liquid chromatography analysis using an optically active column.

[Reference Example 1] Synthesis of {tetrakis (2-oxopyrrolidine-5 (S) -carboxylate)} dirhodium Am. Chem. Soc. 115, 9968 (1993). Under a nitrogen atmosphere, 150 mg (0.34 mmol) of rhodium acetate, 410.7 mg (2.78 mmol) of methyl 2-oxopyrrolidine-5 (S) -carboxylate and 30 mL of dehydrated monochlorobenzene were added to a 50 mL Schlenk tube and heated for 2 hours. Stir. Thereafter, a Soxhlet extractor filled with 2.5 g of sodium carbonate was attached to a 50 mL Schlenk tube, and heated and refluxed for 6 hours while removing the generated acetic acid. The reaction mixture was cooled, concentrated with an evaporator, and purified by column chromatography packed with silica gel (SepraCN). Obtained 180 mg of {tetrakis (2-oxopyrrolidine-5 (S) -carboxylate)} dirhodium as purple crystals (yield 69%).

Reference Example 2 Synthesis of {Tetrakis (4 (S) -methyl-5,5-diphenyl-2-oxazolidinone)} dirhodium In Reference Example 1, 704 mg (2 of methyl 2-oxopyrrolidine-5 (S) -carboxylate .78 mmol) was used in the same manner as in Reference Example 1. {Tetrakis (4 (S) -methyl-5,5-diphenyl-2-oxazolidinone)} 90 mg of rhodium was obtained as purple crystals (yield 21%)

[Example 1]
In a 50 mL Schlenk tube under a nitrogen atmosphere, 19.36 mg (0.025 mmol) of {tetrakis (2-oxopyrrolidine-5 (S) -carboxylate)} dirhodium, and 1-acetoxy-3-methyl-2-butene 2.57 g (20 mmol) was added. The internal temperature was adjusted to 40 ° C., 5 mL of an ethyl acetate solution containing 0.57 g (5 mmol) of ethyl diazoacetate was added dropwise over 6 hours, and the mixture was further stirred and held at the same temperature for 1 hour. Optically active 3-acetoxy An ethyl acetate solution containing ethyl methyl-2,2-dimethylcyclopropanecarboxylate was obtained. Yield: 22%, cis isomer / trans isomer ratio = 90/10, optical purity of cis isomer: 64% e.e. e. .

  In Example 1, as the optically active rhodium compound (1), {tetrakis (4 (S) -methyl-5,5-diphenyl-2-oxazolidinone)} dirhodium (30.38 mg, 0.025 mmol) was used. This was carried out in accordance with Example 1. Yield: 47%, cis isomer / trans isomer ratio = 93/7, optical purity of cis isomer: 35% e.e. e. .

Claims (1)

Formula (1)

(In the formula, R ¹ represents a lower alkoxycarbonyl group, an alkyl group having 1 to 6 carbon atoms, an aryl group or an aralkyl group. R ² and R ³ are the same or different, and each represents a hydrogen atom or a carbon number of 1 to 6). And X represents a carbon or oxygen atom, and * represents an asymmetric carbon.)
In the presence of an optically active rhodium compound represented by formula (2)

(In the formula, R ⁴ represents an alkyl group or an aryl group.)
And diazoacetic acid esters represented by the formula (3)

(In the formula, R ⁵ represents an alkyl group or an aryl group.)
Formula (4) characterized by reacting olefins represented by formula (4)

(In the formula, R ⁴ , R ⁵ and * represent the same meaning as described above.)
A process for producing an optically active cyclopropanecarboxylic acid ester rich in cis-form represented by the formula: