Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

Elliot H. E. Farrar; Matthew N. Grayson

doi:10.1021/acs.joc.2c01039

Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

Elliot H. E. Farrar, Matthew N. Grayson

Department of Chemistry

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

3 Citations (SciVal)

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Abstract

Current models for oxazaborolidine-catalyzed transition-state structures are determined by C–H···O–B and C–H···O═S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C–H···O, C–H···π, and π–π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.

Original language	English
Pages (from-to)	10054–10061
Number of pages	8
Journal	The Journal of Organic Chemistry
Volume	87
Issue number	15
Early online date	18 Jul 2022
DOIs	https://doi.org/10.1021/acs.joc.2c01039
Publication status	Published - 5 Aug 2022

Bibliographical note

Funding Information:
This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. The authors thank the EPSRC, grant numbers EP/R513155/1 (studentship to E.H.E.F.) and EP/W003724/1, and the University of Bath for funding.

ASJC Scopus subject areas

Organic Chemistry

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10.1021/acs.joc.2c01039Licence: CC BY

acs.joc.2c01039Final published version, 6.34 MBLicence: CC BY

Cite this

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title = "Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol",

abstract = "Current models for oxazaborolidine-catalyzed transition-state structures are determined by C–H···O–B and C–H···O═S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C–H···O, C–H···π, and π–π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.",

author = "Farrar, {Elliot H. E.} and Grayson, {Matthew N.}",

note = "Funding Information: This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. The authors thank the EPSRC, grant numbers EP/R513155/1 (studentship to E.H.E.F.) and EP/W003724/1, and the University of Bath for funding. ",

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AU - Farrar, Elliot H. E.

AU - Grayson, Matthew N.

N1 - Funding Information: This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. The authors thank the EPSRC, grant numbers EP/R513155/1 (studentship to E.H.E.F.) and EP/W003724/1, and the University of Bath for funding.

PY - 2022/8/5

Y1 - 2022/8/5

N2 - Current models for oxazaborolidine-catalyzed transition-state structures are determined by C–H···O–B and C–H···O═S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C–H···O, C–H···π, and π–π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.

AB - Current models for oxazaborolidine-catalyzed transition-state structures are determined by C–H···O–B and C–H···O═S formyl hydrogen bonding between the electrophile and catalyst. However, selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol cannot be fully rationalized using these models. Combined density functional theory and noncovalent interaction analyses reveal a new reaction model relying on C–H···O, C–H···π, and π–π interactions between the nucleophile, electrophile, and catalyst to induce selectivity.

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U2 - 10.1021/acs.joc.2c01039

DO - 10.1021/acs.joc.2c01039

M3 - Article

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JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 15

ER -

Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

Abstract

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Machine Learning and Molecular Modelling: A Synergistic Approach to Rapid Reactivity Prediction

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Noncovalent Interactions in the Oxazaborolidine-Catalyzed Enantioselective Mukaiyama Aldol

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

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Machine Learning and Molecular Modelling: A Synergistic Approach to Rapid Reactivity Prediction

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