Nickel-catalyzed direct thiolation of unactivated C(sp<sup>3</sup>)–H bonds with disulfides

Yan, Sheng‐Yi; Liu, Yuejin; Liu, Bin; Liu, Yanhua; Zhang, Zhuo‐Zhuo; Shi, Bing‐Feng

doi:10.1039/c5cc01436k

Cited by 133 publications

(34 citation statements)

References 69 publications

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“…[94] Va rious groups also simultaneously reported CÀH thiolation using the same directing group. [95] Thes ynthesis of nitrogen heterocycles from amides can also be catalyzed by nickel(II). As demonstrated by Ge and co-workers,inthe absence of an exogenous partner to trap the nickel-alkyl intermediate,r eductive elimination can occur to give b-lactam 194 (Scheme 34).…”

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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“…Qiu, Xu and Yin showed that NiBr2 with a bulky carboxylate ligand and sodium carbonate base was most effective, and here phosphine ligands gave slightly lower yields (Scheme 14c). [42] The reaction scope was somewhat broader compared to B.-F. Shi's study, [41] as benzylic and alkyl disulfides could be used while maintaining good yields, though the same α-disubstitution was critical. Again, radical scavengers did not impact the reaction yield.…”

Section: C-s Bond Forming Reactionsmentioning

confidence: 95%

“…B.-F. Shi then showed the sulfide formation with disulfides could be promoted by [Ni(dppp)2Cl]2 using silver oxide and potassium trifluoroacetate additives with a BINOL ligand (Scheme 14b). [41] α-Disubstitution of the propanamide was required, though α-phenyl and α-cyclic aliphatic groups were tolerated. Aromatic disulfides had much improved reactivity, however diethyl disulfide could be used as a coupling partner to afford the ethyl sulfide in low (15%) yield.…”

Section: C-s Bond Forming Reactionsmentioning

confidence: 99%

Base Metal Catalysis in Directed C(sp³)−H Functionalisation

John‐Campbell¹,

Bull²

2019

Adv Synth Catal

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Directed C(sp 3)-H functionalization has made enormous progress in recent years, but has largely been restricted to catalysis using noble metals, particularly palladium. However, since 2013, there have been prominent advances that exploit the reactivity of abundant first row transition metals for a multitude of new bond formations. The use of base metal catalysis for C-H functionalization can provide huge advantages in terms of cost and sustainability compared to methods using noble metals. This review covers all examples, to end 2018, of auxiliary assisted, base metal catalyzed C(sp 3)-H functionalization reactions. Successful examples are reported with Fe, Co, Ni and Cu catalysis with monodentate or bidentate directing groups for C-N, CO , C-S and CC bond forming reactions. This review aims to highlight the current state of this field and potential for expansion and so scope and limitations are highlighted. Notably, examples to date have required sterically activated α-disubstituted substrates, particularly propanamide derivatives with bidentate directing groups, such as 8-aminoquinoline amides. Monodentate quinoline and thioamide directing groups have also been used with Co catalysis for C-N and CC bond formations. Mechanistic details are provided to outline the nature of the proposed organometallic intermediates and potential reaction pathways. We hope this review will stimulate further development in this growing and important field.

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“…Around the same time, Shi also developed the Ni(II)-catalyzed thiolation of C (sp 3 )-H bonds in aliphatic amides with diaryl disulfides (Scheme 27) [54]. Mechanistic experiments using 1,4-dinitrobenzene, TEMPO, and 1,4-diphenylethylene indicated that a thioaryl radical is not involved in the reaction.…”

Section: C-s Bond Formationmentioning

confidence: 97%

Nickel-Catalyzed C–H Bond Functionalization Utilizing an N,N′-Bidentate Directing Group

Chatani

2015

Topics in Organometallic Chemistry

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Nickel-catalyzed direct thiolation of unactivated C(sp³)–H bonds with disulfides

Cited by 133 publications

References 69 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

Base Metal Catalysis in Directed C(sp³)−H Functionalisation

Nickel-Catalyzed C–H Bond Functionalization Utilizing an N,N′-Bidentate Directing Group

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Nickel-catalyzed direct thiolation of unactivated C(sp3)–H bonds with disulfides

Cited by 133 publications

References 69 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

Base Metal Catalysis in Directed C(sp3)−H Functionalisation

Nickel-Catalyzed C–H Bond Functionalization Utilizing an N,N′-Bidentate Directing Group

Contact Info

Product

Resources

About

Nickel-catalyzed direct thiolation of unactivated C(sp³)–H bonds with disulfides

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

Base Metal Catalysis in Directed C(sp³)−H Functionalisation