Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution
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DOI:
10.1055/s-0037-1610309
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发表时间:
2018-10
期刊:
Synthesis
影响因子:
--
通讯作者:
W. Xue;M. Oestreich
W. Xue;M. Oestreich
中科院分区:
其他
文献类型:
--
作者:
W. Xue;M. Oestreich

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摘要广泛的过渡金属催化剂能促进烯丙基亲电试剂与硅格氏试剂的烯丙基取代反应。进一步阐述了以CuI为催化剂的反应过程。区域选择性地独立于初级烯丙基前体的离开基团,倾向于α而不是γ。用环状体系探讨了这种烯丙基转位的立体化学过程,得到了反非对映选择性。
Abstract A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti-diastereoselectivity was obtained.