The Directed ortho‐Metallation (DoM) Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl‐Aryl and Aryl‐Heteroatom‐Aryl Bonds

Anctil, Eric J.‐G.; Snieckus, Victor

doi:10.1002/9783527619535.ch14

Cited by 71 publications

(21 citation statements)

References 144 publications

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“…[8] Examples include Heck reactions, [9] Sonogashira couplings, [10] a-arylations of carbonyl compounds, [11] and couplings initiated by catalytic ortho-metallation steps (Scheme 1). [12] Unfortunately, most of these transformations proceed regiospecifically only for a limited range of substrate types.…”

Section: Introductionmentioning

confidence: 99%

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Gooßen

Linder

Rodríguez

et al. 2009

Chemistry A European J

128

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A bimetallic catalyst system has been developed that for the first time allows the decarboxylative cross-coupling of aryl and acyl carboxylates with aryl triflates. In contrast to aryl halides, these electrophiles give rise to non-coordinating anions as byproducts, which do not interfere with the decarboxylation step that leads to the generation of the carbon nucleophilic cross-coupling partner. As a result, the scope of carboxylate substrates usable in this transformation was extended from ortho-substituted or otherwise activated derivatives to a broad range of ortho-, meta-, and para-substituted aromatic carboxylates. Two alternative protocols have been optimized, one involving heating the substrates in the presence of Cu(I)/1,10-phenanthroline (10-15 mol %) and PdI(2)/phosphine (2-3 mol %) in NMP for 1-24 h, the other involving Cu(I)/1,10-phenanthroline (6-15 mol %) and PdBr(2)/Tol-BINAP (2 mol %) in NMP using microwave heating for 5-10 min. While most products are accessible using standard heating, the use of microwave irradiation was found to be beneficial especially for the conversion of non-activated carboxylates with functionalized aryl triflates. The synthetic utility of the transformation is demonstrated with 48 examples showing the scope and limitations of both protocols. In mechanistic studies, the special role of microwave irradiation is elucidated, and further perspectives of decarboxylative cross-couplings are discussed.

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Section: Introductionmentioning

confidence: 99%

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Gooßen

Linder

Rodríguez

et al. 2009

Chemistry A European J

128

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“…DMBA represents a very good model to put the later Li pincer chemistry into perspective. It was one of the early examples of a molecule that readily undergoes what is now termed "Directed ortho-Metalation" (DoM) [44][45][46][47][48][49][50][51][52][53]. This class of reactions was first described by Gilman in the late 1930s in his seminal investigations into the lithiation of anisole and other aromatic ethers ( [54], also see (Li-Br exchange): [55]).…”

Section: Introduction: Early Studies On Lithium Metal Reagentsmentioning

confidence: 98%

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

Gossage

2015

The Privileged Pincer-Metal Platform: Coordination Chemistry &Amp; Applications

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“…Currently, there is no known diastereoselective method for generating variants 1b (R 1 ≠ R 2 ) containing both chiral elements. In this work, we explore the use of directed ortho -lithiation (DoL) in the rapid assembly of mono- and disubstituted BINOL-phosphates and phosphoramides 1 (R 1 and/or R 2 ≠ H), including its use in the diastereoselective synthesis of 1b (R 1 ≠ R 2 ). − …”

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confidence: 99%

Selective Synthesis of C₁-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

et al. 2021

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The Directed ortho‐Metallation (DoM) Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl‐Aryl and Aryl‐Heteroatom‐Aryl Bonds

Cited by 71 publications

References 144 publications

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

Selective Synthesis of C₁-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

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The Directed ortho‐Metallation (DoM) Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl‐Aryl and Aryl‐Heteroatom‐Aryl Bonds

Cited by 71 publications

References 144 publications

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Biaryl and Aryl Ketone Synthesis via Pd‐Catalyzed Decarboxylative Coupling of Carboxylate Salts with Aryl Triflates

Pincer Complexes of Lithium, Sodium, Magnesium and Related Metals: A Discussion of Solution and Solid-State Aggregated Structure and Reactivity

Selective Synthesis of C1-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation

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Selective Synthesis of C₁-Symmetric BINOL-phosphates and P-chiral Phosphoramides Using Directed ortho-Lithiation