期刊
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
卷 2016, 期 32, 页码 5415-5422出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.201600955
关键词
C-H activation; Isomerization; Cross-coupling; Allylic compounds; Nickel
资金
- Technology R&D Program of Jilin, China [20140203003GX]
Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp(2))-H activation by in-situ-formed Ni-0, which is inserted into the C-H bond at the 2-position of the allyl moiety without a directing group. The isomerization of allylarene to 1-propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross-coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp(2))-H activation and represents a new method for the synthesis of 1,1-disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp(2))-H activation and multiple intermolecular 1,2-, 1,3-, and 2,3-hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.
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