RUTHENIUM-PHOSPHINE COMPLEXES

摘要

A ruthenium-phosphine complex is represented by the formula: [RuH1(R-BINAP) m]X n, (I) wherein R-BINAP is a tertiary phosphine represented by formula (II): R is hydrogen or metal; X is ClO4, BF4 or PF6; and when l is 0, then m is 1 and n' is 2, and when l is 1, then m is 2 and n' is 1. Synthesis methods are (a) Ru2 Cl4(R-BINAP)2(N(C2H5)2) reacted with a salt MX where M is Na, K, Li, Mg or Ag in mixed water and methylene chloride in presence of a quaternary ammonium or phosphonium salt as transfer agent, (b) Ru(R-BINAP) (OAc)2 reacted with an acid HX with stirring in mixed methylene chloride and methanol; and (c) RuHCl(R-BINAP)2 reacted with MX in mixed water and methylene chloride in presence of a quaternary ammonium or phosphonium salt, to give complex where l=1, m=2 and n'=1. The complex is used as catalyst in synthesis, especially asymmetric hydrogenation of allyl alcohols, and is effective at pressure even at room temperature, e.g. for making citronellol from geraniol, in high selectivity.