Enantiopure base-metal catalysts for asymmetric catalysis and bis(imino)pyridine iron alkyl complexes for catalysis

摘要

A transition metal-containing compound having a tridentate chiral ligand bound to iron, cobalt, or nickel. The tridentate ligands are bound to the metal via nitrogen, phosphorus, and/or arsenic atoms. The tridentate ligand has a chiral group bound at least one of the nitrogen, phosphorus, and arsenic atoms, and a blocking group may be bound to another one of the nitrogen, phosphorus, and arsenic atoms. The transition metal-containing compound is useful for the catalyzing the asymmetric hydrogenation of olefins.

主权项

1. A transition metal-containing compound, represented by formula (I): or a salt thereof,wherein
M represents a transition metal atom selected from the group consisting of iron and cobalt; each of X1, X2, and X3 represents a nitrogen atom; Y1 represents a chemical bond between X1 and Z1 or a carbon-containing group that links X1 and Z1 represented by —(CH2)m—, where —, in each occurrence, represents the chemical bond to each of X1 and Z1 and m is an integer of 1, 2, 3, 4, 5, or 6; Y2 represents a chemical bond between X2 and Z2 or a carbon-containing group that links X2 and Z2 represented by —(CH2)m—, where—, in each occurrence, represents the chemical bond to each of X2 and Z2 and m is an integer of 1, 2, 3, 4, 5, or 6; each of Z1 and Z2 represents a chiral group represented by formula (II) or a blocking group selected from the group consisting of an isopropyl group; a tert-butyl group; a neopentyl group; a cyclopropyl group; a cyclobutyl group; a cyclopentyl group; a cyclohexyl group optionally substituted with at least one methyl group, at least one ethyl group, at least one isopropyl group, at least one tert-butyl group, or a combination thereof; a phenyl group optionally substituted with at least one methyl group, at least one ethyl group, at least one isopropyl group, at least one a tert-butyl group, or a combination thereof; an adamantyl group; a trimethylsilyl group; a triethylsilyl group; a tripropylsilyl group; a tri-iso-propyl silyl group; a tri-tert-butyl group; and a neosilyl group, with the proviso that at least one of Z1 and Z2 represents a chiral group represented by formula (II): wherein each of R6 and R7, individually, represents C1-20 alkyl group or a C3-20 cycloalkyl group, with the proviso that R6 and R7 do not simultaneously represent the same group, C* represents a nonracemic chiral carbon atom, and C* is bound to the Y1 or Y2 group or bound to X1 or X2 when Y1 or Y2 represents a chemical bond; n represents an integer of 1; each R1, individually, represents a chemical bond to a carbon atom of Z1 or Z2, a hydrogen atom, a C1-20 alkyl group, or a halogen atom; each of R2 and R5, individually, represents a C1-20 alkyl; R3 and R4, together, form an aromatic ring having five carbon atoms.