Modular Access to Chiral α-(Hetero)aryl Amines via Ni/Photoredox-Catalyzed Enantioselective Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(19), С. 8797 - 8806

Опубликована: Май 3, 2022

Chiral α-aryl N-heterocycles are commonly found in natural products, pharmaceutical agents, and chiral catalysts but remain challenging to access via asymmetric catalysis. Herein, we report a general modular approach for the direct enantioselective α-arylation of saturated azacycles acyclic N-alkyl benzamides nickel/photoredox dual This process exploits hydrogen atom transfer ability photoeliminated chlorine radicals convert corresponding α-amino alkyl that then coupled with ubiquitous inexpensive (hetero)aryl chlorides. These coupling reactions require no oxidants or organometallic reagents, feature feedstock starting materials, broad substrate scope, high enantioselectivities, applicable late-stage diversification medicinally relevant complex molecules. Mechanistic studies suggest nickel catalyst uncommonly plays multiple roles, accomplishing radical generation, capture, cross-coupling, induction.

Язык: Английский

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Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(18), С. 8347 - 8354

Опубликована: Апрель 28, 2022

Grignard addition is one of the most important methods used for syntheses alcohol compounds and has been known over a hundred years. However, research on asymmetric catalysis relies use organometallic nucleophiles. Here, we report first visible-light-induced cobalt-catalyzed reductive Grignard-type synthesizing chiral benzyl alcohols (>50 examples, up to 99% yield, ee). This methodology advantages mild reaction conditions, good functionality tolerance, excellent enantiocontrol, avoidance mass metal wastes, precious catalysts. Kinetic realization studies suggested that migratory insertion an aryl cobalt species into aldehyde was rate-determining step reaction.

Язык: Английский

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Electrophotocatalytic Decoupled Radical Relay Enables Highly Efficient and Enantioselective Benzylic C–H Functionalization

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(47), С. 21674 - 21682

Опубликована: Ноя. 17, 2022

Asymmetric sp3 C–H functionalization has been demonstrated to substantially expedite target molecule synthesis, spanning from feedstocks upgradation late-stage modification of complex molecules. Herein, we report a highly efficient and sustainable method for enantioselective benzylic cyanation by merging electrophoto- copper catalysis. A novel catalytic system allows one independently regulate the hydrogen atom transfer step radical formation speciation Cu(II)/Cu(I) effectively capture transient intermediate, through tuning electronic property anthraquinone-type photocatalyst simply modulating applied current, respectively. Such decoupled relay catalysis enables unified approach diverse alkylarenes, many which are much less reactive or even unreactive using existing relying on coupled relay. Moreover, current protocol is also amenable bioactive molecules, including natural products drugs.

Язык: Английский

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Enantioselective Radical Trifluoromethylation of Benzylic C–H Bonds via Cooperative Photoredox and Copper Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(30), С. 13468 - 13474

Опубликована: Июль 21, 2022

The first enantioselective radical trifluoromethylation of benzylic C–H bonds has been established by a cooperative photoredox and copper catalysis system, providing straightforward access to structurally diverse products in good yields with excellent enantioselectivities under mild conditions. Our method features broad substrate scope functional group compatibility. Merging the is essential for reaction, where used generation radicals from alkyl arenes through hydrogen atom transfer process radicals.

Язык: Английский

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Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(12), С. 6944 - 6952

Опубликована: Март 15, 2023

Enantioselective metallaphotoredox catalysis, which combines photoredox catalysis and asymmetric transition-metal has become an effective approach to achieve stereoconvergence under mild conditions. Although many impressive synthetic approaches have been developed access central chirality, the construction of axial chirality by still remains underexplored. Herein, we report two visible light-induced cobalt-catalyzed reductive couplings biaryl dialdehydes synthesize axially chiral aldehydes (60 examples, up 98% yield, >19:1 dr, >99% ee). This protocol shows good functional group tolerance, broad substrate scope, excellent diastereo- enantioselectivity.

Язык: Английский

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Copper-decorated covalent organic framework as a heterogeneous photocatalyst for phosphorylation of terminal alkynes

Green Chemistry, Год журнала: 2022, Номер 24(10), С. 4071 - 4081

Опубликована: Янв. 1, 2022

A copper decorated covalent organic framework has been prepared and identified as an efficient heterogeneous photocatalyst for the phosphorylation of terminal alkynes.

Язык: Английский

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Photoinduced copper-catalyzed enantioselective coupling reactions

Chemical Society Reviews, Год журнала: 2023, Номер 52(7), С. 2358 - 2376

Опубликована: Янв. 1, 2023

This review highlights the progress in photoinduced copper-catalyzed enantioselective coupling reactions.

Язык: Английский

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Dynamic Kinetic Reductive Conjugate Addition for Construction of Axial Chirality Enabled by Synergistic Photoredox/Cobalt Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 7983 - 7991

Опубликована: Март 28, 2023

Conjugate addition is among the most important synthetic protocols for constructing carbon skeletons and widely used to synthesize natural products drugs. However, asymmetric catalysis studies have mainly focused on stereogenic centers arising from conjugate alkenes. Here, we report first photoinduced cobalt-catalyzed dynamic kinetic reductive reaction that enables formation of heterobiaryls with axial chirality (45 examples, up 91% yield 97% ee). This method features mild conditions, good functional-group tolerance, excellent enantiomeric control. Significantly, large amounts metal waste precious catalysts can be avoided under these conditions. Migration chiral arylcobalt species into alkene might rate-determining step based studies.

Язык: Английский

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Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 9, 2023

Abstract Site- and enantioselective cross-coupling of saturated N -heterocycles carboxylic acids—two the most abundant versatile functionalities—to form pharmaceutically relevant α-acylated amine derivatives remains a major challenge in organic synthesis. Here, we report general strategy for highly site- α-acylation with situ-activated acids. This modular approach exploits hydrogen-atom-transfer reactivity photocatalytically generated chlorine radicals combination asymmetric nickel catalysis to selectively functionalize cyclic α-amino C−H bonds presence benzylic, allylic, acyclic α-amino, α-oxy methylene groups. The mild scalable protocol requires no organometallic reagents, displays excellent chemo-, enantioselectivity, is amenable late-stage diversification, including synthesis previously inaccessible Taxol derivatives. Mechanistic studies highlight exceptional versatility chiral catalyst orchestrating (i) catalytic elimination, (ii) alkyl radical capture, (iii) cross-coupling, (iv) induction.

Язык: Английский

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Catalysts driving efficiency and innovation in thermal reactions: A comprehensive review

Green Technologies and Sustainability, Год журнала: 2024, Номер 2(2), С. 100078 - 100078

Опубликована: Фев. 17, 2024

Язык: Английский

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