H-Cu-P络合物在有机合成中的应用

本文综述了HCuPPh₃]₆的合成方法及氢-铜-膦化合物在有机合成中的应用。作为还原剂，HCuPPh₃]₆可选择性地还原α,β-不饱和酸酯、酮、醛、硝基化合物、腈中的碳碳双键,炔烃中碳碳三键；作为催化剂，可促进氢气、硅氢化合物对上述化合物中碳-碳不饱和键的还原。改变膦配体的结构后的铜-氢-膦化合物可催化对上述化合物中碳碳双键或α,β-不饱和醛、酮、烷基芳基酮中羰基的选择性还原反应。采用合适的手性膦配体，已实现了对上述前手性底物中碳-碳双键、羰基的高对映选择性还原。氢-铜-膦化合物独特的反应及催化性能已用于天然产物及有重要生物活性的化合物的合成中。

The Application of H-Cu-P Complexes in Organic Synthesis

A survey of the literature up to Febrary 2008 on the progress of the preparation of HCuPPh₃]₆ and the application of copper hydride-organo phosphine complexes in organic synthesis is presented in this article. As a reductant, HCuPPh₃]₆ can selectively reduce the C=C double bond in α,β-unsaturated ester, ketone, aldehyde, nitro and nitrile compounds by hydrogen or silane. The C≡C triple bond in alkyne; as a catalyst, it can promote the reduction of C=C double bonds of aforementioned compounds by hydrogen or silane. The C=C double bond in these compounds or carbonyl group in α,β-unsaturated ketone and aldehyde, alkyl aryl and ketone can be selectively reduced by changing the phosphorous ligand. By employing suitable chiral phosphorous ligands, high enantioselective reductions of the C=C double bond, C=O double bond in prochiral substrates have been achieved. The special reactivity and catalytic activity have been utilized in the synthesis of structurally complex natural products and compounds of bioligical importance.