Copper-Catalyzed Asymmetric Alkylation of Secondary Phosphines via Rapid Pyramidal Inversion in P-Stereogenic Cu–Phosphido Intermediates
Copper-Catalyzed Asymmetric Alkylation of Secondary Phosphines via Rapid Pyramidal Inversion in P-Stereogenic Cu–Phosphido Intermediates
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DOI：
10.1021/acs.organomet.2c00218
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发表时间：
2022-06
期刊：
影响因子：
2.8
通讯作者：
Sarah K. Gallant;Ryan M. Tipker;David S. Glueck
中科院分区：
文献类型：
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作者：
Sarah K. Gallant;Ryan M. Tipker;David S. Glueck
金属催化的不对称合成P-立体膦的发展一直受到金属-膦中间体中快速发生锥体反转的假设的指导，但这一过程尚未直接观察到所有感兴趣的金属。我们报道了一个对映选择性的铜（Josiphos）催化的仲膦烷基化反应和反应中间体的观察，包括变温NMR研究了关键的P-立体异构末端膦配合物Cu（diphos*）（PRR′）中磷的低势垒锥体反转，以及研究了它们从仲膦硅烷醇配合物Cu（diphos*）[PHR（R′）]（OSiMe 3）的可逆形成。
Development of metal-catalyzed asymmetric synthesis of P-stereogenic phosphines has been guided by the hypothesis that pyramidal inversion occurs rapidly in metal–phosphido intermediates, but this process has not been observed directly for all metals of interest. We report an enantioselective copper(Josiphos)-catalyzed alkylation of secondary phosphines and observation of the reaction intermediates, including variable temperature NMR studies of low-barrier pyramidal inversion at phosphorus in the key P-stereogenic terminal phosphido complexes Cu(diphos*)(PRR′), and an investigation of their reversible formation from secondary phosphine–silanolate complexes Cu(diphos*)[PHR(R′)](OSiMe3).