Arylboronic acid-catalyzed racemization of secondary and tertiary alcohols

Gregory Boyce; Stefania F. Musolino; Jianing Yang; Andrew D. Smith; James Taylor

doi:10.1021/acs.joc.2c01602

Arylboronic acid-catalyzed racemization of secondary and tertiary alcohols

Gregory Boyce
, Stefania F. Musolino
, Jianing Yang
, Andrew D. Smith^*
, James Taylor

^*Corresponding author for this work

School of Chemistry

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

Abstract

The use of 2-carboxyphenylboronic acid (5 mol %) and oxalic acid (10 mol %) with 2-butanone as a solvent for the racemization of a range of enantiomerically pure secondary and tertiary alcohols is demonstrated. The process is postulated to proceed via reversible Brønsted acid-catalyzed C–O bond cleavage through an achiral carbocation intermediate.

Original language	English
Pages (from-to)	13367-13374
Number of pages	8
Journal	The Journal of Organic Chemistry
Volume	87
Issue number	19
Early online date	8 Sept 2022
DOIs	https://doi.org/10.1021/acs.joc.2c01602
Publication status	Published - 7 Oct 2022

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Boyce_2022_JOC_Arylboronic_CC
Copyright © 2022 The Authors. Published by American Chemical Society. Open Access. This article is distributed under the terms of the Creative Commons Attribution 4.0 License (https://creativecommons.org/licenses/by/4.0/) which permits any use, reproduction and distribution of the work without further permission provided the original work is attributed
Final published version, 1.65 MBLicence: CC BY

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CRITICAT - EASiCAT Studentship: CRITICAT - EASiCAT Studentship
Smith, A. (PI)
EPSRC
1/04/21 → 31/10/22
Project: Standard
Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols
Taylor, J. (PI)
Leverhulme Trust
1/05/15 → 30/04/18
Project: Fellowship
Clean catalysis for sustainable develop: Clean catalysis for sustainable development
Smith, A. (PI)
EPSRC
1/11/12 → 31/10/17
Project: Standard

data underpinning "Arylboronic Acid-Catalyzed Dehydrative Racemization of Secondary and Tertiary Alcohols"
Smith, A. D. (Creator), Boyce, G. (Owner), Taylor, J. (Creator) & Musolino, S. F. (Creator), University of St Andrews, 13 Sept 2022
DOI: 10.17630/32d1c9e3-d14e-4653-98a1-3a5f13cb408c
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@article{9b2d632e00eb4279a6987be99ae36ec7,

title = "Arylboronic acid-catalyzed racemization of secondary and tertiary alcohols",

abstract = "The use of 2-carboxyphenylboronic acid (5 mol \%) and oxalic acid (10 mol \%) with 2-butanone as a solvent for the racemization of a range of enantiomerically pure secondary and tertiary alcohols is demonstrated. The process is postulated to proceed via reversible Br{\o}nsted acid-catalyzed C–O bond cleavage through an achiral carbocation intermediate.",

author = "Gregory Boyce and Musolino, \{Stefania F.\} and Jianing Yang and Smith, \{Andrew D.\} and James Taylor",

note = "Funding: Florida Gulf Coast University; University of St Andrews; UK Engineering and Physical Sciences Research Council - EP/J018139/1, EP/L016419/1, EP/V051423/1; Leverhulme Trust - ECF-2014-005.",

year = "2022",

month = oct,

day = "7",

doi = "10.1021/acs.joc.2c01602",

language = "English",

volume = "87",

pages = "13367--13374",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

number = "19",

}

TY - JOUR

T1 - Arylboronic acid-catalyzed racemization of secondary and tertiary alcohols

AU - Boyce, Gregory

AU - Musolino, Stefania F.

AU - Yang, Jianing

AU - Smith, Andrew D.

AU - Taylor, James

N1 - Funding: Florida Gulf Coast University; University of St Andrews; UK Engineering and Physical Sciences Research Council - EP/J018139/1, EP/L016419/1, EP/V051423/1; Leverhulme Trust - ECF-2014-005.

PY - 2022/10/7

Y1 - 2022/10/7

N2 - The use of 2-carboxyphenylboronic acid (5 mol %) and oxalic acid (10 mol %) with 2-butanone as a solvent for the racemization of a range of enantiomerically pure secondary and tertiary alcohols is demonstrated. The process is postulated to proceed via reversible Brønsted acid-catalyzed C–O bond cleavage through an achiral carbocation intermediate.

AB - The use of 2-carboxyphenylboronic acid (5 mol %) and oxalic acid (10 mol %) with 2-butanone as a solvent for the racemization of a range of enantiomerically pure secondary and tertiary alcohols is demonstrated. The process is postulated to proceed via reversible Brønsted acid-catalyzed C–O bond cleavage through an achiral carbocation intermediate.

U2 - 10.1021/acs.joc.2c01602

DO - 10.1021/acs.joc.2c01602

M3 - Article

SN - 0022-3263

VL - 87

SP - 13367

EP - 13374

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 19

ER -

Arylboronic acid-catalyzed racemization of secondary and tertiary alcohols

Abstract

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Projects

CRITICAT - EASiCAT Studentship: CRITICAT - EASiCAT Studentship

Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

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data underpinning "Arylboronic Acid-Catalyzed Dehydrative Racemization of Secondary and Tertiary Alcohols"

Cite this