Catalytic enantioselective desymmetrizing functionalization of alkyl radicals via Cu(i)/CPA cooperative catalysis

Cheng, Yuan; Liu, Ji-Ren; Gu, Qiang‐Shuai; Yu, Zhang‐Long; Wang, Jian; Li, Zhongliang; Bian, Jun-Qian; Wen, Han-Tao; Wang, Xiaojing; Hong, Xin; Liu, Xinyuan

doi:10.1038/s41929-020-0439-8

Cited by 76 publications

(30 citation statements)

References 59 publications

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“…The addition of the alkyl radical to a diene affords an allylic radical (C) which can react with copper (II) species (B) to deliver the chiral product and regenerate the copper catalyst (I) (A). Due to the complexity of copper chemistry, it is unclear whether the reaction involves a copper (III) species or proceeds through a ligand transfer pathway 3,5,6,45,[53][54][55][56][57] experiments, externally added carboxylic acids rather than in-situ generated carboxylic acid groups, also show high priority towards esterification in the reported cases (Fig. 6a).…”

Section: Resultsmentioning

confidence: 96%

“…Asymmetric carbooxygenative difunctionalization of C-C double bonds is an efficient reaction that simultaneously incorporates two functionalities and can quickly build complex molecules from bulk chemicals [34][35][36][37][38][39][40][41][42][43][44][45][46] . In the category of radical asymmetric transformations, Buchwald et al developed a two-component asymmetric oxyfunctionalization of alkenes with intramolecular carboxylic acid groups 36,37,40 , and Liu et al reported enantioselective oxyfunctionalization of alkenes with linked alcohols and oximes 39,41,44,45 . These reports provide a solution to the long-standing unresolved problems concerning the stereocontrol of acyclic radicals, but with intramolecular oxygen functionalities.…”

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confidence: 99%

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Asymmetric radical carboesterification of dienes

et al. 2021

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The straightforward strategy of building a chiral C-O bond directly on a general carbon radical center is challenging and stereocontrol of the reactions of open-chain hydrocarbon radicals remains a largely unsolved problem. Advance in this elementary step will spur the development of asymmetric radical C-O bond construction. Herein, we report a copper-catalyzed regioselective and enantioselective carboesterification of substituted dienes using alkyl diacyl peroxides as the source of both the carbon and oxygen substituents. The participation of external acids in this reaction substantially extends its applicability and leads to structurally diverse allylic ester products. This work represents the advance in the key elementary reaction of intermolecular enantioselective construction of C-O bond on open-chain hydrocarbon radicals and may lead to the discovery of other asymmetric radical reactions.

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Section: Resultsmentioning

confidence: 96%

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confidence: 99%

Asymmetric radical carboesterification of dienes

et al. 2021

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“…Another breakthrough has been the achievement of enantioconvergent functionalization of racemic tertiary C(sp 3 )-H bonds (pK a > 25) by Arnold's and Liu's groups using mutated enzymes 82 , and Liu's group using Cu(I)/CPA catalysts [83][84][85] , respectively. The challenge for developing such a transformation mainly rests on the issue of chirality retention, which is common to most of the C(sp 3 )-H functionalization methods based on the transition metal-catalyzed C-H activation, the concerted metal carbenoid/nitrenoid C-H insertion, or the coupled enantiodiscriminative HAA/stereoretentive RR mechanistic manifolds.…”

Section: Reactions With Enantiodetermining Radical Functionalizationmentioning

confidence: 99%

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Zhang

et al. 2021

Nat Commun

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114

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Recently, with the boosted development of radical chemistry, enantioselective functionalization of C(sp3)–H bonds via a radical pathway has witnessed a renaissance. In principle, two distinct catalytic modes, distinguished by the steps in which the stereochemistry is determined (the radical formation step or the radical functionalization step), can be devised. This Perspective discusses the state-of-the-art in the area of catalytic enantioselective C(sp3)–H functionalization involving radical intermediates as well as future challenges and opportunities.

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“…Later, Liu developed a general and efficient catalytic enantioselective desymmetrizing functionalization of alkyl radicals generated in situ from alkene‐tethered 1,3‐diols via Cu(I)/SPA cooperative catalysis (Scheme 75). [ 79 ] This method provides various tetrahydrofurans and analogues bearing multiple stereocentres with remarkably high levels of enantio‐ and diastereocontrol. Theory calculations and mechanistic experiments revealed a possible mechanism involving an enantiodetermining outer‐sphere C—O bond formation step.…”

Section: Asymmetric Metal‐organic Cooperative Catalysismentioning

confidence: 99%

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

et al. 2021

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What is the most favorite and original chemistry developed in your research group? Developing SPINOL-phosphoric acids (SPAs), TM-SPINOL-phosphoric acids (SPAs 2.0) and PCP-derived planar chiral phosphoric acids (PPAs) for asymmetric catalysis. What is the most important personality for scientific research? Curiosity, optimism, self-confidence and persistence. What's your hobbies? What's your favorite book(s)? I enjoy cooking. My favorite book is Journey to the West. Who influences you mostly in your life? My mother. What is your favorite journal(s)? The journals publishing the original and systematic work of synthetic chemistry. Could you please give us some advices on improving Chinese Journal of Chemistry? Fast review, fast publication, fast promotion via new media.

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Catalytic enantioselective desymmetrizing functionalization of alkyl radicals via Cu(i)/CPA cooperative catalysis

Cited by 76 publications

References 59 publications

Asymmetric radical carboesterification of dienes

Asymmetric radical carboesterification of dienes

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

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