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

Elliot H. E. Farrar; Matthew N. Grayson

doi:10.1021/acs.joc.0c02226

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

Elliot H. E. Farrar, Matthew N. Grayson

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

5 Citations (SciVal)

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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.

Original language	English
Pages (from-to)	15449–15456
Journal	Journal of Organic Chemistry
Volume	85
Issue number	23
Early online date	23 Nov 2020
DOIs	https://doi.org/10.1021/acs.joc.0c02226
Publication status	Published - 4 Dec 2020

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10.1021/acs.joc.0c02226Licence: CC BY

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acs.joc.0c02226Final published version, 3.18 MBLicence: CC BY

Dataset for "Computational Modelling and Machine Learning Approaches Towards Understanding Asymmetric Catalytic Organic Reactions"
Farrar, E. (Creator) & Grayson, M. (Supervisor), University of Bath, 12 Aug 2022
DOI: 10.15125/BATH-01148
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title = "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 Br{\o}nsted 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.",

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AU - Farrar, Elliot H. E.

AU - Grayson, Matthew N.

PY - 2020/12/4

Y1 - 2020/12/4

N2 - 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.

AB - 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.

U2 - 10.1021/acs.joc.0c02226

DO - 10.1021/acs.joc.0c02226

M3 - Article

SN - 0022-3263

VL - 85

SP - 15449

EP - 15456

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 23

ER -

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

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