Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters

Matthew J. Hesse; Stephanie Essafi; Charlotte G. Watson; Jeremy N. Harvey; David Hirst; Christine L. Willis; Varinder K. Aggarwal

doi:10.1002/anie.201402995

Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters

Matthew J. Hesse, Stephanie Essafi, Charlotte G. Watson, Jeremy N. Harvey, David Hirst, Christine L. Willis, Varinder K. Aggarwal^*

^*Corresponding author for this work

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

43 Citations (Scopus)

302 Downloads (Pure)

Abstract

alpha,alpha-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of beta-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereo-selective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.

Original language	English
Pages (from-to)	6145-6149
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	24
Early online date	5 May 2014
DOIs	https://doi.org/10.1002/anie.201402995
Publication status	Published - 5 May 2014

Structured keywords

BCS and TECS CDTs

Keywords

alkenes
allylation
asymmetric synthesis
C-C coupling
synthetic methods
ORIENTED ORGANIC-SYNTHESIS
OXIDATIVE HECK ARYLATION
STEREOSELECTIVE-SYNTHESIS
TETRASUBSTITUTED ALKENES
ENANTIOSELECTIVE SYNTHESIS
HOMOALLYLIC ALCOHOLS
DIASTEREOSELECTIVE SYNTHESIS
SECONDARY ALCOHOLS
REACTION SEQUENCE
INTERNAL ALKYNES

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10.1002/anie.201402995

MHesse_ACIE_2014Accepted author manuscript, 790 KB

http://onlinelibrary.wiley.com/doi/10.1002/anie.201402995/abstract

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3-month Core Capability for Chemistry Research
Crosby, J.
1/01/13 → 1/04/13
Project: Research
Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis
Aggarwal, V. K.
14/05/12 → 13/01/18
Project: Research

Cite this

@article{53a23fc4345140e39fbeb1230a030aff,

title = "Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters",

abstract = "alpha,alpha-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of beta-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereo-selective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.",

keywords = "alkenes, allylation, asymmetric synthesis, C-C coupling, synthetic methods, ORIENTED ORGANIC-SYNTHESIS, OXIDATIVE HECK ARYLATION, STEREOSELECTIVE-SYNTHESIS, TETRASUBSTITUTED ALKENES, ENANTIOSELECTIVE SYNTHESIS, HOMOALLYLIC ALCOHOLS, DIASTEREOSELECTIVE SYNTHESIS, SECONDARY ALCOHOLS, REACTION SEQUENCE, INTERNAL ALKYNES",

author = "Hesse, {Matthew J.} and Stephanie Essafi and Watson, {Charlotte G.} and Harvey, {Jeremy N.} and David Hirst and Willis, {Christine L.} and Aggarwal, {Varinder K.}",

year = "2014",

month = may,

day = "5",

doi = "10.1002/anie.201402995",

language = "English",

volume = "53",

pages = "6145--6149",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "Wiley-VCH Verlag",

number = "24",

}

TY - JOUR

T1 - Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters

AU - Hesse, Matthew J.

AU - Essafi, Stephanie

AU - Watson, Charlotte G.

AU - Harvey, Jeremy N.

AU - Hirst, David

AU - Willis, Christine L.

AU - Aggarwal, Varinder K.

PY - 2014/5/5

Y1 - 2014/5/5

N2 - alpha,alpha-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of beta-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereo-selective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.

AB - alpha,alpha-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of beta-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereo-selective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.

KW - alkenes

KW - allylation

KW - asymmetric synthesis

KW - C-C coupling

KW - synthetic methods

KW - ORIENTED ORGANIC-SYNTHESIS

KW - OXIDATIVE HECK ARYLATION

KW - STEREOSELECTIVE-SYNTHESIS

KW - TETRASUBSTITUTED ALKENES

KW - ENANTIOSELECTIVE SYNTHESIS

KW - HOMOALLYLIC ALCOHOLS

KW - DIASTEREOSELECTIVE SYNTHESIS

KW - SECONDARY ALCOHOLS

KW - REACTION SEQUENCE

KW - INTERNAL ALKYNES

U2 - 10.1002/anie.201402995

DO - 10.1002/anie.201402995

M3 - Article (Academic Journal)

C2 - 24799283

VL - 53

SP - 6145

EP - 6149

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 24

ER -

Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters

Abstract

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Keywords

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3-month Core Capability for Chemistry Research

Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis

Cite this