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

Snieckus, Victor; Anctil, Eric J.‐G.

doi:10.1002/9783527655588.ch14

Cited by 6 publications

(3 citation statements)

References 243 publications

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“…Classically, the Me 2 N group induces ortho / para ‐selective electrophilic aromatic substitution (S E Ar) reactions when directly attached to an aromatic ring 1. Through the strong complex‐induced proximity effect with organolithium reagents, the Me 2 N group features prominently in directed ortho ‐metalation (D o M) reactions of aromatics 2–6. In a similar fashion, a range of transition‐metal‐catalyzed CH functionalization reactions (D o CH) are known to be directed by the Me 2 N group 7–16.…”

Section: Methodsmentioning

confidence: 99%

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Zhang

Hagihara

Itami

2015

Chemistry A European J

119

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The dimethylamino (Me2N) group is arguably the most versatile functional group capable of highly efficient and site-selective directed aromatic functionalizations at the ortho-, meta-, and para-positions depending on reaction conditions. While the repertoire of Me2N-directed reactions is growing at a rapid pace, the lack of a general method to transform this group to other functionalities hampers its wider application in organic synthesis. Here we report nickel-catalyzed C-N borylations of aryl- and benzyl-dimethylamines that permit the conversion of a huge library of largely underutilized Me2N-containing organic molecules into various functional molecules by taking advantage of the wealth of existing C-B functionalization methods.

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Section: Methodsmentioning

confidence: 99%

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Zhang

Hagihara

Itami

2015

Chemistry A European J

119

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“…The availability of the 2,7-dibromo and 2,7-diiodo naphthalene dicarboxamides 4e and 4f , and the knowledge of arylated naphthalene diamides as significant materials in solar-cell research, compelled us to attempt bis Suzuki–Miyaura cross-coupling chemistry . To start, the 2-iodo- N , N -diethyl-naphthalene-1,8-dicarboxyamide 3b was subjected to coupling with selected aryl boronic acids under optimized conditions (10 mol % Pd(PPh 3 ) 4 /K 3 PO 4 /anhyd DMF) to afford products 5a – f in consistently higher yields (Scheme ).…”

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confidence: 99%

Directed Ortho and Remote Metalation of Naphthalene 1,8-Diamide: Complementing S_EAr Reactivity for the Synthesis of Substituted Naphthalenes

et al. 2021

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Mono- and dianion species of 1,8-naphthalene diamide 2 were generated under sec-BuLi/TMEDA conditions and trapped with a variety of electrophiles to give 2- and 2,7- substituted products 3 and 4. Using Suzuki–Miyaura cross-coupling, mono- and di-iodinated products were converted into the corresponding 2-aryl (5) and 2,7-diaryl (6) products, respectively. The amide–amide rotation barrier of 2 was established by VT NMR, and the structure of fluorenone structure 9, obtained by remote metalation, was secured.

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“…Aryl tertiary amines, e.g., N , N -dialkylaniline, are typically functionalized at the ortho and para positions via well-known electrophilic aromatic substitution (S E Ar) reactions . Meanwhile, ortho -selective C–H functionalization of aryl tertiary amines could also proceed via directed ortho metalation (D o M) reactions by means of the complex-induced proximity effect with organolithium reagents or via transition-metal-catalyzed ortho -C–H functionalization with the dialkylamino group as a directing group . Relatively, catalytic meta -selective C–H functionalization of aryl tertiary amines is greatly limited by their intrinsic electron biases .…”

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confidence: 99%

Palladium(II)-Catalyzed Remotemeta-C–H Functionalization of Aromatic Tertiary Amines

Wang

Zhou

et al. 2019

Org. Lett.

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Pd(II)-catalyzed remote C−H olefination of aromatic tertiary amines was achieved with high meta selectivity. With the assistance of an elaborated template, C−H functionalization of unreactive aryl tertiary amines, hindered by the p−π conjugation between the lone-pair electrons of the nitrogen atom and the phenyl ring, was realized with high meta regioselectivity via a quaternary ammonium salt assembly. The results demonstrate that apart from the distance and geometry of the template, the conformation of the arene substrate also plays a crucial role in the templated-assisted remote C−H functionalization.

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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 6 publications

References 243 publications

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Directed Ortho and Remote Metalation of Naphthalene 1,8-Diamide: Complementing S_EAr Reactivity for the Synthesis of Substituted Naphthalenes

Palladium(II)-Catalyzed Remotemeta-C–H Functionalization of Aromatic Tertiary Amines

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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 6 publications

References 243 publications

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Making Dimethylamino a Transformable Directing Group by Nickel‐Catalyzed CN Borylation

Directed Ortho and Remote Metalation of Naphthalene 1,8-Diamide: Complementing SEAr Reactivity for the Synthesis of Substituted Naphthalenes

Palladium(II)-Catalyzed Remotemeta-C–H Functionalization of Aromatic Tertiary Amines

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Product

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About

Directed Ortho and Remote Metalation of Naphthalene 1,8-Diamide: Complementing S_EAr Reactivity for the Synthesis of Substituted Naphthalenes