Highly Regioselective Copper‐Catalyzed Benzylic CH Amination by <i>N</i>‐Fluorobenzenesulfonimide

Ni, Zhikun; Zhang, Qian; Xiong, Tao; Zheng, Yiying; Li, Yan; Zhang, Hongwei; Zhang, Jingping; Li, Qun

doi:10.1002/anie.201107427

Cited by 219 publications

(82 citation statements)

References 33 publications

(38 reference statements)

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“…In each of the reactions in Fig. 2A, small quantities (trace – 12%) of benzylimide product derived from coupling with the bis(sulfonyl)imide of NFSI (30) were detected by 1 H NMR.…”

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confidence: 99%

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Zhang

Wang

McCann

et al. 2016

Science

529

328

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Direct methods for stereoselective functionalization of C(sp3)–H bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. Here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic C–H bonds into benzylic nitriles. Hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric C(sp3)–CN bond upon reaction with a chiral copper catalyst. The reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90-99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. Mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and C–H oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways.

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“…In each of the reactions in Fig. 2A, small quantities (trace – 12%) of benzylimide product derived from coupling with the bis(sulfonyl)imide of NFSI (30) were detected by 1 H NMR.…”

mentioning

confidence: 99%

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Zhang

Wang

McCann

et al. 2016

Science

529

328

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“…This suggests the formation of a rather unstable copper(III) species, which has been previously reported for the reaction of copper(II) with F-TEDA-BF 4 . 6c,6d,26 The structure of a complex obtained by mixing copper(II) trifluoroacetylacetonate and F-TEDA-BF 4 has been previously characterized by X-ray crystallography, 27 but all attempts to identify a similar structure starting with CuBr 2 failed. However, crystalline H-TEDA-BF 4 was isolated after mixing F-TEDA-BF 4 and CuBr 2 in MeCN and the resulting salt was characterized by X-ray crystallography (see SI for details), suggesting that hydrogen abstraction occurred on the solvent.…”

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confidence: 99%

Intermolecular Ritter-Type C–H Amination of Unactivated sp³ Carbons

2012

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Intermolecular Ritter-type C–H amination of unactivated sp3 carbons has been developed. This new reaction proceeds under mild conditions using readily available reagents and an inexpensive source of nitrogen (acetonitrile). A broad scope of substrates can be aminated with this method since many functional groups are tolerated. This reaction also allows for the direct, innate C–H amination of a variety of hydrocarbons such as cyclohexane without the need of prefunctionalization or installation of a directing group.

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“…Noteworthy are original contributions by Zhang 82 on the use of NFSI for the amide-directed, palladium-catalyzed C–H amination of N -phenylacetamides selectively at the ortho, para, or benzylic (for N-p -tolylacetamides) position. The benzylic amination was further elaborated by Zhang and Liu 83 with copper-mediated systems that remarkably favor primary over secondary benzylic sites. These seminal contributions are not reviewed further, since they fall outside the scope of the present review.…”

Section: Pertinent Examples Of Catalytic Amination Of Benzenesmentioning

confidence: 99%

Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

Stavropoulos

2016

Comments on Inorganic Chemistry

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Highly Regioselective Copper‐Catalyzed Benzylic CH Amination by N‐Fluorobenzenesulfonimide

Cited by 219 publications

References 33 publications

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Intermolecular Ritter-Type C–H Amination of Unactivated sp³ Carbons

Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

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Highly Regioselective Copper‐Catalyzed Benzylic CH Amination by N‐Fluorobenzenesulfonimide

Cited by 219 publications

References 33 publications

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay

Intermolecular Ritter-Type C–H Amination of Unactivated sp3 Carbons

Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

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Product

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Intermolecular Ritter-Type C–H Amination of Unactivated sp³ Carbons