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Computational Studies of Chiral Hydroxyl Carboxylic Acids: The Allylboration of Aldehydes.

ABSTRACT: The mechanism of the asymmetric BINOL-derived hydroxyl carboxylic acid catalyzed allylboration of benzaldehyde was investigated using density functional theory calculations. A new reaction model is proposed, and the roles of the two Brønsted acidic sites of the catalyst elucidated. Catalyst distortion was found to be a key factor in determining stereoselectivity. The flexibility of the hydroxyl carboxylic acid catalyst leads to significant differences in the mechanism and origins of selectivity compared to the equivalent phosphoric acid catalyzed reaction.

SUBMITTER: Farrar EHE

PROVIDER: S-EPMC7735727 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

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Computational Studies of Chiral Hydroxyl Carboxylic Acids: The Allylboration of Aldehydes.

Farrar Elliot H E EHE Grayson Matthew N MN

The Journal of organic chemistry 20201123 23

The mechanism of the asymmetric BINOL-derived hydroxyl carboxylic acid catalyzed allylboration of benzaldehyde was investigated using density functional theory calculations. A new reaction model is proposed, and the roles of the two Brønsted acidic sites of the catalyst elucidated. Catalyst distortion was found to be a key factor in determining stereoselectivity. The flexibility of the hydroxyl carboxylic acid catalyst leads to significant differences in the mechanism and origins of selectivity ...[more]

PMID: 33227201

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