| 摘要 |
Chiral asymmetrical bidentate organo-phosphorus ligands with a bicycloaliphatic framework are new. Chiral asymmetrical bidentate organo-phosphorus ligands with a bicycloaliphatic framework are of formula (I). [Image] Independent claims are also included for: (i) complexes of (I) with transition metal-salts or -complexes, especially complexes of formula (II); and (ii) preparation of phosphine-phosphonite and diphosphine compounds of formula (I). [MxPyLzSq]Ar (II) m and n : 0 or 1; R1> and R2>1-24C alkyl, 3-8C cycloalkyl (optionally with 1 or 2 of the C atoms in the ring replaced by N, O or S heteroatoms), 2-13C heteroaryl with 1-4 N, O or S heteroatoms, 6-14C aryl, phenyl, naphthyl or fluorenyl, where (a) these groups are each optionally substituted by one or more of the following groups : H, 1-20C alkyl, 2-20C alkenyl, 1-10C haloalkyl, 3-8C cycloalkyl, 2-9C heterocycloalkyl with 1-4 N, O or S heteroatoms, 6-8C aryl, phenyl, naphthyl, fluorenyl, 2-6C heteroaryl with 1-4 N, O or S heteroatoms, 1-10C alkoxy, 1-9C trihalomethylalkyl, halo, OH, trifluoromethylsulfonato, oxo, amino, -NH-alkyl, -NH-aryl, -N-(alkyl)2, -N-(aryl)2, -N+>-(alkyl)3, -N+>-(aryl)3, -NH-CO-alkyl or -NH-CO-aryl (these 8 amino or amido groups having alkyls of 1-8C and aryls of 5 or 6C), CN, COOH, COOQ (Q = monovalent cation or 1-8C alkyl), 1-6C acyloxy, sulfinato, -SO3H, -SO3Q' (Q' = monovalent cation, 1-8C alkyl or 6C aryl), -PO3H2, -PO3HQ', -PO3(Q') 2 or tri-1-6C alkylsilyl; and (b) both R1> or both R2> are bridged to each other such that the resulting rings can be substituted by 1-10C alkyl or alkoxy, 6C aryl, benzyl, OH or benzyloxy groups; R3> - R1>0>H, 1-24C alkyl, 1-10C haloalkyl, 3-8C cycloalk(en)yl (optionally with 1 or 2 of the C atoms in the ring replaced by N, O or S heteroatoms), 6-14C aryl, phenyl, naphthyl, fluorenyl or 2-13C heteroaryl with 1-4 N, O or S heteroatoms, where these groups are each optionally substituted by one or more of the following groups : H, 1-20C alkyl, 2-20C alkenyl, 1-10C haloalkyl, 3-8C cycloalk(en)yl, 1-9C heterocycloalk(en)yl, 6-8C aryl, phenyl, naphthyl, fluorenyl, 2-6C heteroaryl with 1-4 N, O or S heteroatoms, 1-10C alkoxy, CF3, F, OH, oxo, amino, -N-(alkyl)2, -N-(aryl)2, -N+>-(alkyl)3 or -N+>-(aryl)3 (these 4 amino groups having alkyls of 1-8C and aryls of 5 or 6C), optionally with 2 such substituents being linked by bridging; P : trivalent phosphorus; M : a transition metal central atom; L : coordinated (in)organic ligand; S : coordinated solvent molecule; A : equivalent of a non-coordinated anion; x : 1 or 2; y >= 1; z, q and r = 0 or positive integers; y + z + q = a value limited by the co-ordination centers but not all co-ordination positions need be used; and P' in (II) = a ligand of formula (I). |
