Optically active 2-allylcarboxylic acid derivative and process for producing the same

A process for producing an optically active 2-allylcarboxylic acid represented by the following formula (5);

• wherein R4 represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms and *2 indicates that the carbon atom marked therewith is an asymmetric carbon atom;,
• which comprises:
• (a) reacting a carboxamide compound represented by the following formula (2);
• wherein R1 and R2 each independently represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms, R4 is as defined above and * 1 indicates that the carbon atom marked therewith is an asymmetric carbon atom;
• with an organometallic compound and then further with a compound represented by the formula;
• ClCOOR5
• wherein R5 represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms;
• to give a 2-allylcarboxamide derivative represented by the following formula (3);
• wherein R1, R2, R4, R5, *1 and *2 are as defined above;,
• (b) reacting the derivative (3) with a compound represented by the formula MOR6 wherein M represents an alkali metal and R6 represents a substituted or unsubstituted alkyl group containing 1 to 20 carbon atoms
• to give a 2-allylcarboxylic acid ester derivative represented by the following formula (4);
• wherein R4, R6 and *2 are as defined above;,
• and
• (c) further hydrolyzing the derivative (4).

A process for producing a 2-allylcarboxamide derivative represented by the following formula (6);

• wherein R1, R2 and R4 each independently represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms and *1 and *2 each indicates that the carbon atom marked therewith is an asymmetric carbon atom;,
• which comprises reacting a carboxamide compound represented by the following formula (2)
• wherein R1, R2, R4 and *1 are as defined above;
• with an organometallic compound.

A process for producing a 2-allylcarboxamide derivative represented by the following formula (3);

• wherein R1, R2, R4 and R5 each independently represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms, and *1 and *2 each indicates that the carbon atom marked therewith is an asymmetric carbon atom;
• which comprises reacting a compound represented by the following formula (6);
• wherein R1, R2, R4, *1 and *2 are as defined above;
• in the presence of a base and further with a compound represented by the formula;
• ClCOOR5
• wherein R5 is as defined above.

A process for producing a 2-allylcarboxamide derivative represented by the following formula (3);

• wherein R1, R2, R4 and R5 each independently represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms, and *1 and *2 each indicates that the carbon atom marked therewith is an asymmetric carbon atom;
• which comprises reacting a carboxamide compound represented by the following formula (2);
• wherein R1, R2, R4 and *1 are as defined above;
• with an organometallic compound and further with a compound represented by the formula;
• ClCOOR5
• wherein R5 is as defined above.

A process for producing a 2-allylcarboxylic acid represented by the following formula (8);

• wherein R4 represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms, R9 represents a hydrogen atom or a substituted or unsubstituted alkyl group containing 1 to 20 carbon atoms, and * indicates that the carbon atom marked therewith is an asymmetric carbon atom or an ester derivative thereof;,
• which comprises reacting a 2-allylcarboxamide derivative represented by the following formula (7);
• wherein R4 is as defined hereinabove, R7 and R8 each represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms and R7 and R8 may be bound together to form a ring, X represents C, S or S(O), Y represents CH, O or NH and * is as defined hereinabove;
• with a compound represented by the formula MOR9
• wherein M represents an alkali metal and R9 is as defined hereinabove and,
• if necessary, hydrolyzing the resulting ester.

A process for producing an optically active 2-allylcarboxylic acid represented by the following formula (5);

• wherein R4 represents a substituted or unsubstituted alkyl group containing 1 to 18 carbon atoms, a substituted or unsubstituted aryl group containing 6 to 20 carbon atoms or a substituted or unsubstituted aralkyl group containing 7 to 20 carbon atoms, and *2 indicates that the carbon atom marked therewith is an asymmetric carbon atom;
• which comprises causing an enzyme source having asymmetric hydrolysis activity to act on a 2-allylcarboxylic acid ester derivative represented by the following formula (4);
• wherein R4 is as defined hereinabove, R6 represents a substituted or unsubstituted alkyl group containing 1 to 20 carbon atoms, and *2 is as defined hereinabove;
• and
• collecting the resulting optically active 2-allylcarboxylic acid.