Chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof

摘要

The present invention relates to a chiral spiro-pyridylamidophosphine ligand compound, synthesis method therefor and application thereof. The chiral spiro-pyridylamidophosphine compound is a compound having a structure of Formula (I), a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, and is mainly characterized by having a chiral spiro-dihydro-indene skeleton in its structure. The chiral spiro-pyridylamidophosphine compound may be synthesized with optical active 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene or substituted 7-diaryl/alkylphosphino-7′-amino-1,1′-spiro-dihydro-indene having a spiro-skeleton as chiral starting material. The chiral spiro-pyridylamidophosphine compound may be used as a chiral ligand in asymmetric hydrogenation of a carbonyl compound catalyzed by iridium, in which the reaction activity is very high, the amount of the catalyst may be 0.0001 mol %, and the enantioselectivity of the reaction is up to 99.9% ee.;

主权项

1. Chiral spiro-pyridylamidophosphine compound having the structure of Formula (I), or a racemate or optical isomer thereof, or a catalytically acceptable salt thereof, wherein, R1 is C1-C8 chain hydrocarbyl or saturated cyclic hydrocarbyl or cycloalkenyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, furyl or thienyl, and the substituent on said substituted phenyl is halogen, C1-C8 hydrocarbyl or alkoxy, with a substituent amount of 1-5, and said heteroaryl is pyridyl;
R2, R3, R4 and R5 are H, C1-C8 alkyl or alkoxy, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, furyl or thienyl, and the substituent on said substituted phenyl is C1-C8 alkyl or alkoxy, with a substituent amount of 1-5, and said heteroaryl is pyridyl; or R2 and R3, R4 and R5 are incorporated into C3-C7 aliphatic ring or aromatic ring, respectively; R2, R3, R4 and R5 can be the same or different;R6, R7 are H, C1-C8 alkyl, C1-C8 alkoxy, C1-C8 aliphatic amido group, and n=0-3; or when n≧2, two adjacent R6 groups or two adjacent R7 groups can be incorporated into C3-C7 aliphatic ring or aromatic ring, and R6, R7 can be the same or different;R8, R9 are H, halogen, C1-C8 alkyl, C1-C8 alkoxy, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, furyl or thienyl, and the substituent on said substituted phenyl is halogen, C1-C8 alkyl or alkoxy, with a substituent amount of 1-5, and said heteroaryl is pyridyl, and m=0-3; or when m≧2, adjacent R9 or R8 and R9 groups can be incorporated into C3-C7 aliphatic ring or aromatic ring, and R8, R9 can be the same or different;R10 is H, C1-C8 alkyl, phenyl, substituted phenyl, 1-naphthyl, 2-naphthyl, heteroaryl, furyl or thienyl, and the substituent on said substituted phenyl is C1-C8 hydrocarbyl or alkoxy, with a substituent amount of 1-5, and said heteroaryl is pyridyl.