Gold-Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross-Coupling Reactivity with Gold

A sp3–sp2 CC cross‐coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetalation...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 53; no. 24; pp. 6211 - 6215
Main Authors Levin, Mark D., Toste, F. Dean
Format Journal Article
LanguageEnglish
Published Weinheim WILEY-VCH Verlag 10.06.2014
WILEY‐VCH Verlag
Wiley
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Acids
allylation
bimetallic catalysis
Bimetals
Boronic Acids - chemistry
Catalysis
Catalysts
Chemistry
Chemistry, Multidisciplinary
CC coupling
Gold
Gold - chemistry
gold catalysis
Mathematical models
Oxidants
oxidative addition
Oxidizing agents
Physical Sciences
Proposals
Science & Technology
Teaching
Transformations
C-C coupling
ORGANOGOLD COMPLEXES
ISOMERIZATION
<AU(CH2)2PPH2>2
BOND FORMATION
gold catalysis
REDUCTIVE ELIMINATION
OXYARYLATION
REARRANGEMENT
DINUCLEAR GOLD(I)
allylation
oxidative addition
METHYL-IODIDE
bimetallic catalysis
CC coupling
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Summary:A sp3–sp2 CC cross‐coupling reaction catalyzed by gold in the absence of a sacrificial oxidant is described. Vital to the success of this method is the implementation of a bimetallic catalyst bearing a bis(phosphino)amine ligand. A mechanistic hypothesis is presented, and observable transmetalation, CBr oxidative addition, and CC reductive elimination in a model gold complex are shown. We expect that this method will serve as a platform for the development of novel transformations involving redox‐active gold catalysts. Teaching Au new tricks: A novel manifold for reactivity in gold catalysis has been realized, allowing the cross‐coupling of arylboronic acids and allylic bromides without a sacrificial oxidant. A bimetallic catalyst is employed, providing allylbenzene products with unique scope and chemoselectivity. A mechanistic proposal is put forward based on stoichiometric experiments, including the isolation of an AuIII allyl complex.
Bibliography:We gratefully acknowledge NIHGMS (RO1 GM073932) for financial support. M.D.L. thanks the NSF GRFP and ARCS foundation for graduate research fellowships. We gratefully acknowledge Dr. Yi-Ming Wang, Andrew V. Samant, and Dr. David A. Nagib for helpful discussion, and Dr. Antonio DiPasquale for assistance with collecting and analyzing crystallographic data. Prof. Neal P. Mankad is thanked for initial investigations into the chemistry of 1 and 8.
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ArticleID:ANIE201402924
NIHGMS - No. RO1 GM073932
We gratefully acknowledge NIHGMS (RO1 GM073932) for financial support. M.D.L. thanks the NSF GRFP and ARCS foundation for graduate research fellowships. We gratefully acknowledge Dr. Yi‐Ming Wang, Andrew V. Samant, and Dr. David A. Nagib for helpful discussion, and Dr. Antonio DiPasquale for assistance with collecting and analyzing crystallographic data. Prof. Neal P. Mankad is thanked for initial investigations into the chemistry of
8
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NIH RePORTER
ObjectType-Article-1
SourceType-Scholarly Journals-1
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content type line 23
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201402924