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Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity.

ABSTRACT: The Simmons-Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal-carbon multiple bonds. Herein, we describe this type of reaction and the construction of three-membered rings has now been applied in organometallic systems by combining classical zinc carbenoid reagents with a range of structurally and electronically diverse metal carbynes. A variety of metallacyclopropene derivatives prepared in this way represent rare examples with σ-aromaticity in an unsaturated three-membered ring. The structures of such products are supported by experimental observations and theoretical calculations.

SUBMITTER: Huang F

PROVIDER: S-EPMC8162146 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature

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Extension of the Simmons-Smith reaction to metal-carbynes: efficient synthesis of metallacyclopropenes with σ-aromaticity.

Huang Fanping F Zheng Xuejuan X Lin Xinlei X Ding Linting L Zhuo Qingde Q Wen Ting Bin TB Zhang Hong H Xia Haiping H

Chemical science 20200903 37

The Simmons-Smith reaction offers a direct route for conversion of an alkene into a cyclopropane with a zinc carbenoid as the active intermediate. Zinc carbenoids, however, have never delivered a methylene unit to substrates with metal-carbon multiple bonds. Herein, we describe this type of reaction and the construction of three-membered rings has now been applied in organometallic systems by combining classical zinc carbenoid reagents with a range of structurally and electronically diverse meta ...[more]

PMID: 34094279

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