Allylic substitution by carbon nucleophiles on 4-bromo-4-methyl-2-pentenoate: anti-michael regioselectivity

Add time:09/08/2019    Source:sciencedirect.com

The reaction of carbanions α-to nitriles with tertiary bromoester 1 does not give cyclopropanes, whatever the reaction conditions, while Li enolate of methyl phenylacetate does, in THF or THF-Et2O. From lithiated aminonitriles 5, in THF-HMPA, the reaction leads to a mixture of SN and SN' products in equal amounts via a radical process. From arylaceto- and propionitriles 4 whatever the conditions, and from methyl phenylacetate enolate 16, either associated to Li in THF-HMPA or to K in THF, SN' anti-Michaël products are predominantly formed via a concerted inner sphere process, showing thus the possibility of a polar-SET mechanistic spectrum from a single electrophilic reagent.

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