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Review
. 2017 Jul 7;2017(25):3517-3527.
doi: 10.1002/ejoc.201700121. Epub 2017 Apr 26.

Recent Progress in Decarboxylative Oxidative Cross-Coupling for Biaryl Synthesis

Gregory J P Perry  1 , Igor Larrosa  1
Affiliations
Review

Recent Progress in Decarboxylative Oxidative Cross-Coupling for Biaryl Synthesis

Gregory J P Perry et al. European J Org Chem. .

Abstract

The beginning of the 21st century has seen tremendous growth in the field of decarboxylative activation. Benzoic acid derivatives are now recognised as atom-economic alternatives to traditional cross-coupling partners, and they also benefit from being inexpensive, readily available and shelf-stable reagents. In this microreview we discuss recent developments in the coupling of benzoic acid derivatives either with an arene or with a second benzoic acid derivative, a process often termed decarboxylative oxidative cross-coupling. These procedures offer great promise for the development of highly selective and atom-economic cross-couplings.

Keywords: Biaryls; Cross‐coupling; C–H activation; Decarboxylation; Oxidative Coupling.

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Figures

Scheme 1
Scheme 1
Timeline of significant advancements in decarboxylative oxidative couplings for biaryl synthesis.
Scheme 2
Scheme 2
Copper‐catalysed protodecarboxylation of aromatic acids. [a] 3a (10 mol‐%). [b] 3b (10 mol‐%).
Scheme 3
Scheme 3
Palladium‐catalysed/promoted protodecarboxylation of aromatic acids.
Scheme 4
Scheme 4
Silver‐catalysed protodecarboxylation of aromatic acids. [a] 160 °C. [b] AcOH (5 mol‐%).
Scheme 5
Scheme 5
Silver‐catalysed protodecarboxylation of aromatic acids under radical conditions. [a] AgOAc (40 mol‐%).
Scheme 6
Scheme 6
Proposed mechanism for the silver‐catalysed protodecarboxylation of aromatic acids under radical conditions.
Scheme 7
Scheme 7
(i) General mechanism for the transition‐metal‐promoted decarboxylation of benzoic acid derivatives. (ii) Primary ortho effect (steric destabilisation). (iii) Secondary ortho effect (steric destabilisation + coordination).
Scheme 8
Scheme 8
Scope of the decarboxylative oxidative coupling of 2,6‐dimethoxybenzoic acid with simple arenes. [a] From 2‐phenoxybenzoic acid.
Scheme 9
Scheme 9
Scope of the intramolecular decarboxylative oxidative coupling of 2‐aryloxybenzoic acid derivatives. [a] Asterisk marks position of minor cyclised regioisomer.
Scheme 10
Scheme 10
Scope of the decarboxylative oxidative coupling between indole derivatives and electron‐deficient benzoic acid derivatives.
Scheme 11
Scheme 11
Scope of the decarboxylative oxidative coupling between indole derivatives and electron‐rich or electron‐deficient benzoic acid derivatives.
Scheme 12
Scheme 12
General schematic for the decarboxylative oxidative coupling between benzoic acid derivatives and heteroaromatics. [a] Ag3PO4 (1.5 equiv.), K3PO4 (2.0 equiv.).
Scheme 13
Scheme 13
General schematic for the decarboxylative oxidative coupling between benzoic acid derivatives and simple arenes.
Scheme 14
Scheme 14
General schematic for the decarboxylative oxidative coupling between benzoic acid derivatives and polyfluorinated arenes.
Scheme 15
Scheme 15
General schematic for the decarboxylative oxidative coupling between benzoic acid derivatives and arenes bearing acidic C–H bonds.
Scheme 16
Scheme 16
General schematic for the decarboxylative oxidative coupling of benzoic acid derivatives with arenes bearing acidic C–H bonds.
Scheme 17
Scheme 17
Scope of the decarboxylative oxidative coupling between azolecarboxylic acids and azoles in the presence of a [Pd]/[Cu] system.
Scheme 18
Scheme 18
Scope of the decarboxylative oxidative coupling between 2‐nitrobenzoic acid derivatives and benzoxazole derivatives in the presence of a [Cu]/[Ag] system.
Scheme 19
Scheme 19
Scope of the decarboxylative oxidative coupling of heteroarenes in the presence of a [Cu]‐only system.
Scheme 20
Scheme 20
Scope of the directed decarboxylative oxidative coupling between benzamide derivatives and thiophenecarboxylic acid derivatives in the presence of a [Cu]/[Ag] system. PIP = (pyridin‐2‐yl)isopropyl. [a] Yield of bis(arylated) product. Asterisk marks the position of bis(arylation).
Scheme 21
Scheme 21
Scope of the decarboxylative oxidative coupling between 2‐nitrobenzoic acid derivatives and (benz)oxazole derivatives in the presence of an [Ni]/[Ag] system. [a] Ag2CO3 (3.0 equiv.); no BQ added.
Scheme 22
Scheme 22
Scope of the decarboxylative oxidative coupling under radical conditions in the presence of an [Ag]‐only system.
Scheme 23
Scheme 23
Scope of the double decarboxylative homocoupling of benzoic acid derivatives in the presence of a [Pd]/[Ag] system.
Scheme 24
Scheme 24
Scope of the double decarboxylative homocoupling of benzoic acid derivatives in the presence of a [Cu]‐only system.
Scheme 25
Scheme 25
Scope of the double decarboxylative cross‐coupling of benzoic acid derivatives in the presence of a [Pd]/[Ag] system.
Scheme 26
Scheme 26
Scope of the double decarboxylative cross‐coupling of benzoic acid derivatives in the presence of a [Pd]/[Ag] system: an improved system.
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