Catalyst composition and process for producing cross-coupled compound using same
A catalyst composition for a cross-coupling reaction comprising a nickel salt-amine complex of formula (1), and triphenylphosphine. where R 1 thru R 4 independently represent alkyl, aryl, heteroaryl or alkenyl; n is an integer of 1-6; and X independently represents halo, hydroxyl, nitrate or acetate group. Using the catalyst composition, a cross-coupling reaction is carried out between a boron-containing compound of formula (2) and a compound of formula (3). where R 5 and R 6 are the same as R 1 -R 4 defined above; Y independently represents hydroxyl or alkoxy, Z is halo, methanesulfonate or trifluoromethanesulfonate.
1. A process for producing a cross-coupled compound represented by the following formula (4):
R 5 —R 6 (4)
wherein R 5 and R 6 may be the same or different and represent a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group; which comprises allowing a boron-containing compound represented by the following formula (2) to react with a compound represented by the following formula (3):
wherein R 5 and R 6 are as defined above; Y may be the same or different and each Y represents a hydroxyl group or an alkoxy group, provided that, when each Y is a hydroxyl group, three boron-containing compounds may be dehydration-condensed to form a trimer anhydride, and that, when two Y are an alkoxy group, the two Y may be bonded together to form a ring; and Z represents a halogen atom, a methanesulfonate group or a trifluoromethane-sulfonate group; in the presence of a base and a catalyst composition for a cross-coupling reaction comprising a complex of a nickel salt with an amine compound, represented by the following formula (1), and triphenylphosphine
wherein R 1 through R 4 may be the same or different and represent a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group; n is an integer of 1 to 6; and X may be the same or different and each X represents a halogen atom, a hydroxyl group, a nitrate group or an acetate group.
2. The process for producing a cross-coupled compound according to claim 1 , wherein the base is a carbonic acid salt compound.
3. The process for producing a cross-coupled compound according to claim 2 , wherein the boron-containing compound of formula (2) is an aromatic boron-containing compound represented by the following formula (5) or an alkenyl boron-containing compound represented by the following formula (6);
wherein R 7 through R 10 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 7 s bonded to two adjacent carbon atoms on the benzene ring in the formula (5) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 8 and R 10 on the alkenyl group in the formula (6) may be bonded together to form a ring, and R 9 and R 10 bonded to the same carbon atom on the alkenyl group in the formula (6) may be bonded together to form a ring; a is an integer of 1 to 5; and Y may be the same or different and each Y represents a hydroxyl group or an alkoxy group.
4. The process for producing a cross-coupled compound according to claim 3 , wherein the compound of the formula (3) is an aromatic compound represented by the following formula (7) or an alkanyl compound represented by the following formula (8):
wherein R 11 through R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 11 s bonded to two adjacent carbon atoms on the benzene ring in the formula (7) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 12 and R 14 on the alkenyl group in the formula (8) may be bonded together to form a ring, and R 13 and R 14 bonded to the same carbon atom on the alkenyl group in the formula (8) may be bonded together to form a ring; b is an integer of 1 to 5; and Z represents a halogen atom, a methanesulfonate group or a trifluoromethanesulfonate group.
5. The process for producing a cross-coupled compound according to claim 1 , wherein the boron-containing compound of formula (2) is an aromatic boron-containing compound represented by the following formula (5) or an alkenyl boron-containing compound represented by the following formula (6):
wherein R 7 through R 10 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 7 s bonded to two adjacent carbon atoms on the benzene ring in the formula (5) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 8 and R 10 on the alkenyl group in the formula (6) may be bonded together to form a ring, and R 9 R 10 bonded to the same carbon atom on the alkenyl group in the formula (6) may be bonded together to form a ring; a is an integer of 1 to 5; and Y may be the same or different and each Y represents a hydroxyl group or an alkoxy group.
6. The process for producing a cross-coupled compound according to claim 5 , wherein the compound of the formula (3) is an aromatic compound represented by the following formula (7) or an alkenyl compound represented by the following formula (8):
wherein R 11 through R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 11 s bonded to two adjacent carbon atoms on the benzene ring in the formula (7) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 12 and R 14 on the alkenyl group in the formula (8) may be bonded together to form a ring, and R 13 and R 14 bonded to the same carbon atom on the alkenyl group in the formula (8) may be bonded together to form a ring; b is an integer of 1 to 5; and Z represents a halogen atom, a methanesulfonate group or a trifluoromethanesulfonate group.
7. The process for producing a cross-coupled compound according to claim 1 , wherein the compound of the formula (3) is an aromatic compound represented by the following formula (7) or an alkenyl compound represented by the following formula (8):
wherein R 11 through R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 11 s bonded to two adjacent carbon atoms on the benzene ring in the formula (7) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 12 and R 14 on the alkenyl group in the formula (8) may be bonded together to form a ring, and R 13 and R 14 bonded to the same carbon atom on the alkenyl group in the formula (8) may be bonded together to form a ring; b is an integer of 1 to 5; and Z represents a halogen atom, a methanesulfonate group or a trifluoromethanesulfonate group.
8. The process for producing a cross-coupled compound according to claim 2 , wherein the compound of the formula (3) is an aromatic compound represented by the following formula (7) or an alkenyl compound represented by the following formula (8):
wherein R 11 through R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted linear, branched or cyclic alkenyl group, a hydroxyl group, an alkoxy group, an amino group, a cyano group, a carbonyl group, a carboxyl group or an ester group; provided that two R 11 s bonded to two adjacent carbon atoms on the benzene ring in the formula (7) may be bonded together to form a condensed ring with the benzene ring, and two adjacent R 12 and R 14 on the alkenyl group in the formula (8) may be bonded together to form a ring, and R 13 and R 14 bonded to the same carbon atom on the alkenyl group in the formula (8) may be bonded together to form a ring; b is an integer of 1 to 5; and Z represents a halogen atom, a methanesulfonate group or a trifluoromethanesulfonate group.