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Fe-Catalyzed dicarbofunctionalization of electron-rich alkenes with Grignard reagents and (fluoro)alkyl halides.

ABSTRACT: An iron-catalyzed regioselective dicarbofunctionalization of electron-rich alkenes is described. In particular, aryl- and alkyl vinyl ethers are used as effective linchpins to couple alkyl or (fluoro)alkyl halides and sp²-hybridized Grignard nucleophiles. Preliminary results demonstrate the ability to engage thioethers as linchpins and control enantioselectivity in these transformations, an area which is largely unexplored in iron-catalyzed three-component cross-coupling reactions.

SUBMITTER: Rotella ME

PROVIDER: S-EPMC8722523 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Fe-Catalyzed dicarbofunctionalization of electron-rich alkenes with Grignard reagents and (fluoro)alkyl halides.

Rotella Madeline E ME Sar Dinabandhu D Liu Lei L Gutierrez Osvaldo O

Chemical communications (Cambridge, England) 20211123 93

An iron-catalyzed regioselective dicarbofunctionalization of electron-rich alkenes is described. In particular, aryl- and alkyl vinyl ethers are used as effective linchpins to couple alkyl or (fluoro)alkyl halides and sp<sup>2</sup>-hybridized Grignard nucleophiles. Preliminary results demonstrate the ability to engage thioethers as linchpins and control enantioselectivity in these transformations, an area which is largely unexplored in iron-catalyzed three-component cross-coupling reactions. ...[more]

PMID: 34751287

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Project description:We describe the mechanism, substituent effects, and origins of the selectivity of the nickel-catalyzed four-component coupling reactions of alkyl fluorides, aryl Grignard reagents, and two molecules of 1,3-butadiene that affords a 1,6-octadiene carbon framework bearing alkyl and aryl groups at the 3- and 8-positions, respectively, and the competing cross-coupling reaction. Both the four-component coupling reaction and the cross-coupling reaction are triggered by the formation of anionic nickel complexes, which are generated by the oxidative dimerization of two molecules of 1,3-butadiene on Ni(0) and the subsequent complexation with the aryl Grignard reagents. The C-C bond formation of the alkyl fluorides with the γ-carbon of the anionic nickel complexes leads to the four-component coupling product, whereas the cross-coupling product is yielded via nucleophilic attack of the Ni center toward the alkyl fluorides. These steps are found to be the rate-determining and selectivity-determining steps of the whole catalytic cycle, in which the C-F bond of the alkyl fluorides is activated by the Mg cation rather than a Li or Zn cation. ortho-Substituents of the aryl Grignard reagents suppressed the cross-coupling reaction leading to the selective formation of the four-component products. Such steric effects of the ortho-substituents were clearly demonstrated by crystal structure characterizations of ate complexes and DFT calculations. The electronic effects of the para-substituent of the aryl Grignard reagents on both the selectivity and reaction rates are thoroughly discussed. The present mechanistic study offers new insight into anionic complexes, which are proposed as the key intermediates in catalytic transformations even though detailed mechanisms are not established in many cases, and demonstrates their synthetic utility as promising intermediates for C-C bond forming reactions, providing useful information for developing efficient and straightforward multicomponent reactions.

Dataset Information

Fe-Catalyzed dicarbofunctionalization of electron-rich alkenes with Grignard reagents and (fluoro)alkyl halides.

Publications

Fe-Catalyzed dicarbofunctionalization of electron-rich alkenes with Grignard reagents and (fluoro)alkyl halides.

Similar Datasets

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