Origin of stereocontrol in the Matteson reaction: Importance of attractive electrostatic interactions

Valerio Fasano; Varinder K. Aggarwal

doi:10.1016/j.tet.2020.131810

Origin of stereocontrol in the Matteson reaction: Importance of attractive electrostatic interactions

Valerio Fasano, Varinder K. Aggarwal^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

Abstract

The Matteson reaction involves treatment of a chiral boronic ester with (dichloromethyl)lithium in the presence of ZnCl2 which leads to an α–chloroboronic ester with very high diastereoselectivity. The origin of selectivity has now been investigated using modern computational analysis. The explanation for selectivity was previously based on steric repulsions in the transition state but the new study has identified a novel Cl··H electrostatic interaction which is only present in one of the two possible transition states. It is believed that this attractive interaction is critical in controlling the stereochemical outcome of the process. Furthermore, this more complete model can now be used to rationalize the disparity in reactivity (C–migration vs O–migration) occasionally observed in diastereomeric boron ate complexes, and why substrates devoid of the key hydrogen bond react with low stereocontrol.

Original language	English
Article number	131810
Number of pages	4
Journal	Tetrahedron
Volume	78
Early online date	1 Dec 2020
DOIs	https://doi.org/10.1016/j.tet.2020.131810
Publication status	Published - 8 Jan 2021

Bibliographical note

Funding Information:
V.F. thanks the University of Bristol for awarding the EPSRC Doctoral Prize Fellowship, Grant Ref: EP/R513179/1 . We thank Dr. Beatrice S. L. Collins (UoB) for valuable discussions.

Publisher Copyright:
© 2020 Elsevier Ltd

Keywords

Matteson reaction
1,2-migration
density functional theory
diastereoselectivity
transition state

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title = "Origin of stereocontrol in the Matteson reaction: Importance of attractive electrostatic interactions",

abstract = "The Matteson reaction involves treatment of a chiral boronic ester with (dichloromethyl)lithium in the presence of ZnCl2 which leads to an α–chloroboronic ester with very high diastereoselectivity. The origin of selectivity has now been investigated using modern computational analysis. The explanation for selectivity was previously based on steric repulsions in the transition state but the new study has identified a novel Cl··H electrostatic interaction which is only present in one of the two possible transition states. It is believed that this attractive interaction is critical in controlling the stereochemical outcome of the process. Furthermore, this more complete model can now be used to rationalize the disparity in reactivity (C–migration vs O–migration) occasionally observed in diastereomeric boron ate complexes, and why substrates devoid of the key hydrogen bond react with low stereocontrol.",

keywords = "Matteson reaction, 1,2-migration, density functional theory, diastereoselectivity, transition state",

author = "Valerio Fasano and Aggarwal, {Varinder K.}",

note = "Funding Information: V.F. thanks the University of Bristol for awarding the EPSRC Doctoral Prize Fellowship, Grant Ref: EP/R513179/1 . We thank Dr. Beatrice S. L. Collins (UoB) for valuable discussions. Publisher Copyright: {\textcopyright} 2020 Elsevier Ltd",

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T2 - Importance of attractive electrostatic interactions

AU - Fasano, Valerio

AU - Aggarwal, Varinder K.

N1 - Funding Information: V.F. thanks the University of Bristol for awarding the EPSRC Doctoral Prize Fellowship, Grant Ref: EP/R513179/1 . We thank Dr. Beatrice S. L. Collins (UoB) for valuable discussions. Publisher Copyright: © 2020 Elsevier Ltd

PY - 2021/1/8

Y1 - 2021/1/8

N2 - The Matteson reaction involves treatment of a chiral boronic ester with (dichloromethyl)lithium in the presence of ZnCl2 which leads to an α–chloroboronic ester with very high diastereoselectivity. The origin of selectivity has now been investigated using modern computational analysis. The explanation for selectivity was previously based on steric repulsions in the transition state but the new study has identified a novel Cl··H electrostatic interaction which is only present in one of the two possible transition states. It is believed that this attractive interaction is critical in controlling the stereochemical outcome of the process. Furthermore, this more complete model can now be used to rationalize the disparity in reactivity (C–migration vs O–migration) occasionally observed in diastereomeric boron ate complexes, and why substrates devoid of the key hydrogen bond react with low stereocontrol.

AB - The Matteson reaction involves treatment of a chiral boronic ester with (dichloromethyl)lithium in the presence of ZnCl2 which leads to an α–chloroboronic ester with very high diastereoselectivity. The origin of selectivity has now been investigated using modern computational analysis. The explanation for selectivity was previously based on steric repulsions in the transition state but the new study has identified a novel Cl··H electrostatic interaction which is only present in one of the two possible transition states. It is believed that this attractive interaction is critical in controlling the stereochemical outcome of the process. Furthermore, this more complete model can now be used to rationalize the disparity in reactivity (C–migration vs O–migration) occasionally observed in diastereomeric boron ate complexes, and why substrates devoid of the key hydrogen bond react with low stereocontrol.

KW - Matteson reaction

KW - 1,2-migration

KW - density functional theory

KW - diastereoselectivity

KW - transition state

U2 - 10.1016/j.tet.2020.131810

DO - 10.1016/j.tet.2020.131810

M3 - Article (Academic Journal)

VL - 78

JO - Tetrahedron

JF - Tetrahedron

SN - 0040-4020

M1 - 131810

ER -

Origin of stereocontrol in the Matteson reaction: Importance of attractive electrostatic interactions

Abstract

Bibliographical note

Keywords

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