Nickel-Catalyzed Direct Arylation of C(sp<sup>3</sup>)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance

Aihara, Yoshinori; Chatani, Naoto

doi:10.1021/ja411715v

Cited by 378 publications

(111 citation statements)

References 59 publications

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“…[14] Va rious functionalities can be incorporated into the molecule at these unactivated CÀHb onds.T his is exemplified by initial reports from the groups of Chatani and Ge.B yu sing Ni II as ap recatalyst in conjunction with [91] or alkylation with alkyl iodides. [92] Shi and co-workers showed the Ni II -catalyzed alkenylation of amide 191 with vinyl iodides [93] to afford alkenylated products.Asreported by Zhang and co-workers, alkenylation can also be accomplished with phenylacetylenes.…”

Section: Nickel(ii)mentioning

confidence: 99%

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

2017

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The functionalization of C(sp3)−H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C−H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition‐metal‐catalyzed C−H activation, 1,n‐hydrogen atom transfer, and transition‐metal‐catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp3)−H bonds. For each strategy, the scope, the reactivity of different C−H bonds, the position of the reacting C−H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C−H functionalization reactions and inspire future research in this area.

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Section: Nickel(ii)mentioning

confidence: 99%

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

2017

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“…In the field of chelation-assisted CH functionalization, our group recently reported on the first nickel(II)-catalyzed β-arylation of unactivated CH bonds of aliphatic amides, using an 8-aminoquinoline moiety as the bidentate directing group and iodoarenes as coupling partners. 27 Prior to our discovery, to the best of our knowledge, nickel-catalyzed C(sp 3 )H bond functionalization had been limited to only one example, namely, the Ni(0)-catalyzed cycloaddition of formamides with alkynes. 28 After the determining the optimized reaction conditions, it was found that 157 afforded the desired product 162 in 83% yield with Ni(OTf) 2 as the precatalyst with the aid of a sterically bulky carboxylic acid (MesCO 2 H) and a base (Na 2 CO 3 ) in DMF at 140°C for 24 h (Scheme 9).…”

Section: C(spmentioning

confidence: 99%

Nickel Catalysts/N,N′-Bidentate Directing Groups: An Excellent Partnership in Directed C–H Activation Reactions

2015

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, working on the use of molecular defined iron complexes as catalysts for the selective hydrosilylation of carbonyl compounds. From January 2013, he has been a postdoctoral fellow in the research group of Prof. Naoto Chatani at Osaka University (Japan), where he is focused on the directed CH bond functionalization and CC or Cheteroatom bond formation reactions with transition-metal catalysis. AbstractThis review focuses on chelation-assisted regioselective CH activation with CC or/and CN bond formation using nickel(0) or -(II) as the catalysts, where bidentate directing groups play a key role in the successful transformation. A 2-pyridinylmethylamine or an 8-aminoquinoline moiety are the more powerful auxiliaries among the directing groups examined.

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“…Significant deuterium incorporation was also found at C2',t hus indicating that the nickel(0) system can also activate the N-benzylic position. [15] For 1a to 3a (84 %Y ield), GCMS analysis of the crude reaction mixture revealed the concomitant formation of benzaldehyde in 78 %yield. These observations show that the benzyloxy unit of the acrylate partner (2b)a cts as the reductant for C À Cbond formation.…”

Section: Angewandte Chemiementioning

confidence: 99%

Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel‐Catalyzed Transfer‐Hydrogenative Strategy

2017

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Nickel-catalyzed coupling of benzyl acrylates with activated ketones and imines provides g-butyrolactones and lactams,r espectively.T he benzyl alcohol byproduct released during the lactonization/lactamization event is relayed to the next cycle where it serves as the reductant for CÀCb ond formation. This strategy represents ac onceptually unique approach to transfer-hydrogenative C À Cbond formation, thus providing examples of reductive heterocyclizations where hydrogen embedded within an alcohol leaving group facilitates turnover.The identification of catalytic paradigms for the direct and atom-economical assembly of C À Cb onds is ak ey goal of organic chemistry.Within this context, transfer-hydrogenative C À Cb ond formation has emerged as ap owerful platform for reaction design. Forexample,hydrogen borrowing allows the direct a-alkylation of carbonyl compounds with alcohols by ac atalytic dehydrogenation/condensation/reduction sequence (Scheme 1a).[1] Therelated Guerbet reaction effects the dehydrative union of two alcohols,t hus providing an efficient method to upgrade bioethanol to butanol (Scheme 1b).[2] Krische and co-workers have pioneered transferhydrogenative alcohol CÀHfunctionalizations as exemplified by processes where alcohol dehydrogenation drives the reductive generation of nucleophilic metal allyls in advance of carbonyl addition (Scheme 1c).[3] Each of these reaction classes merges redox events with C À Cb ond formation, thus avoiding stepwise generation of reactive functionality and enhancing substantially atom economy.Assuch, new transferhydrogenative CÀCbond-forming strategies are likely to find wide utility in reaction design.Our studies in this area were initiated by considering synthetic entries to g-butyrolactones and lactams, [4][5][6][7] which are versatile intermediates as well as core motifs in an array of natural products.A na ppealing,y et unrealized approach to these compounds resides in metal-catalyzed reductive coupling of either ac arbonyl or imine with an acrylate to afford a g-amino or g-hydroxy ester,w hich upon cyclization would provide the target (Scheme 1d). This disconnection requires the identification of as trategy which enables reductive CÀC bond formation, but avoids nonproductive reduction of the starting materials.W er easoned that these criteria might be fulfilled by coupling the release of the reductant to the formation of either the lactone or lactam, thereby minimizing nonproductive background reduction events.Such aproposition appears practically challenging,h owever,asimple solution is availed by harnessing the native reducing power of the alcohol released upon cyclization to drive turnover. In this way,t he alcohol byproduct from one cycle is relayed to the next, where it then serves as the reductant for C À Cb ond formation. Herein, as proof-of-concept, we show that lactones and lactams can be generated by nickel-catalyzed union of activated ketones and ketimines,r espectively,w ith O-benzyl acrylates.T his approach provides unique examples of r...

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Nickel-Catalyzed Direct Arylation of C(sp³)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance

Cited by 378 publications

References 59 publications

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Nickel Catalysts/N,N′-Bidentate Directing Groups: An Excellent Partnership in Directed C–H Activation Reactions

Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel‐Catalyzed Transfer‐Hydrogenative Strategy

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Nickel-Catalyzed Direct Arylation of C(sp3)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance

Cited by 378 publications

References 59 publications

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp3)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Nickel Catalysts/N,N′-Bidentate Directing Groups: An Excellent Partnership in Directed C–H Activation Reactions

Reductive Coupling of Acrylates with Ketones and Ketimines by a Nickel‐Catalyzed Transfer‐Hydrogenative Strategy

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Nickel-Catalyzed Direct Arylation of C(sp³)–H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer

Complementary Strategies for Directed C(sp³)−H Functionalization: A Comparison of Transition‐Metal‐Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer