Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines is a potentially useful approach to a class of chiral ligands with valuable applications in asymmetric catalysis. We introduced this idea with chiral platinum and palladium catalysts, exploiting rapid pyramidal inversion in diastereomeric metal–phosphido complexes (ML*(PRR′)) to control phosphorus stereochemistry. This Account summarizes our attempts to develop related synthetic methods using earth-abundant metals, especially copper, in which weaker metal–ligand bonds and faster substitution processes were expected to result in more active catalysts. Indeed, precious metals were not required. Without any transition metals at all, we exploited related P-epimerization processes to prepare enantiomerically pure phosphiranes and secondary phosphine oxides (SPOs) from commercially available chiral epoxides. 1 Introduction 2 Copper-Catalyzed Phosphine Alkylation 3 Copper-Catalyzed Tandem Phosphine Alkylation/Arylation 4 Nickel-Catalyzed Phosphine Alkylation 5 Proton-Mediated P-Epimerization in Synthesis of Chiral Phosphiranes 6 Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides (SPOs) from (+)-Limonene Oxide 7 Conclusions

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P-立体膦的催化不对称合成：超越贵金属

金属催化的 P-立体膦的不对称合成是一类潜在有用的方法，在不对称催化中具有有价值的应用。我们通过手性铂和钯催化剂引入了这一想法，利用非对映金属-磷化物配合物（ML*（PRR'））中的快速锥体反转来控制磷立体化学。本报告总结了我们使用地球上丰富的金属（尤其是铜）开发相关合成方法的尝试，其中较弱的金属 - 配体键和更快的取代过程有望产生更活跃的催化剂。事实上，不需要贵金属。完全没有任何过渡金属，我们利用相关的 P-差向异构化工艺从市售的手性环氧化物制备对映异构纯的膦和仲氧化膦 (SPO)。1 引言 2 铜催化的膦烷基化 3 铜催化的串联膦烷基化/芳基化 4 镍催化的膦烷基化 5 合成手性磷烷中的质子介导的 P-差向异构化 6 非对映选择性合成 P-Steresine 二级生磷+)-氧化柠檬烯 7 结论