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Regioselective molybdenum-catalyzed allylic substitution of tertiary allylic electrophiles: methodology development and applications.

ABSTRACT: The first molybdenum-catalyzed allylic sulfonylation of tertiary allylic electrophiles is described. The method employs a readily accessible catalyst (Mo(CO)₆/2,2'-bipyridine, both are commercially available) and represents the first example of the use of a group 6 transition metal-catalyst for allylic sulfonylation of substituted tertiary allylic electrophiles to form carbon-sulfur bonds. This atom economic and operationally simple methodology is characterized by its relatively mild conditions, wide substrate scope, and excellent regioselectivity profile, thus unlocking a new platform to forge sulfone moieties, even in the context of late-stage functionalization and providing ample opportunities for further derivatization through traditional Suzuki cross-coupling reactions.

SUBMITTER: Salman M

PROVIDER: S-EPMC8159339 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Regioselective molybdenum-catalyzed allylic substitution of tertiary allylic electrophiles: methodology development and applications.

Salman Muhammad M Xu Yaoyao Y Khan Shahid S Zhang Junjie J Khan Ajmal A

Chemical science 20200506 21

The first molybdenum-catalyzed allylic sulfonylation of tertiary allylic electrophiles is described. The method employs a readily accessible catalyst (Mo(CO)<sub>6</sub>/2,2'-bipyridine, both are commercially available) and represents the first example of the use of a group 6 transition metal-catalyst for allylic sulfonylation of substituted tertiary allylic electrophiles to form carbon-sulfur bonds. This atom economic and operationally simple methodology is characterized by its relatively mild ...[more]

PMID: 34094074

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