Highly selective coupling of alkenes and aldehydes catalyzed by [Ni(NHC){P(OPh)3}]:: Synergy between a strong σ donor and a strong π acceptor

Highly selective coupling of alkenes and aldehydes catalyzed by [Ni(NHC){P(OPh)3}]:: Synergy between a strong σ donor and a strong π acceptor
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DOI:
10.1002/anie.200603907
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发表时间:
2007-01-01
影响因子:
16.6
通讯作者:
Jamison, Timothy F.
Jamison, Timothy F.
中科院分区:
化学1区
文献类型:
--
作者:
Ho, Chun-Yu;Jamison, Timothy F.

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强电子给体(IPr)和强电子受体(P(OPh)3)对于烯烃、醛和甲硅烷基三氟甲磺酸酯之间的高选择性镍催化偶联反应都是必需的。在没有亚磷酸酯的情况下,没有观察到催化作用,并且观察到几种副反应。亚磷酸盐似乎抑制这些副产物的形成,并通过加速从(IPr-Ni-H)(OTf)络合物的还原消除来拯救催化循环。
Both a strong electron donor (IPr) and a strong electron acceptor (P(OPh)3) are necessary for a highly selective, nickel-catalyzed coupling reaction between alkenes, aldehydes, and silyltriflates. Without the phosphite, catalysis is not observed and several side reactions are observed. The phosphite appears to suppress the formation of these byproducts and rescue the catalytic cycle by accelerating reductive elimination from an (IPr–Ni–H)(OTf) complex.