Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Language: Английский

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

De Zhong,

Yanmei Lin

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8797 - 8806

Published: May 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.

Language: Английский

Citations

95
Electrophotocatalytic Decoupled Radical Relay Enables Highly Efficient and Enantioselective Benzylic C–H Functionalization DOI
Wenzheng Fan,

Xueyao Zhao,

Yunshun Deng

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(47), P. 21674 - 21682

Published: Nov. 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.

Language: Английский

Citations

92
Photoassisted Cobalt-Catalyzed Asymmetric Reductive Grignard-Type Addition of Aryl Iodides DOI
Xuan‐Feng Jiang, Hao Jiang, Qian Yang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(18), P. 8347 - 8354

Published: April 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.

Language: Английский

Citations

91
Enantioselective Radical Trifluoromethylation of Benzylic C–H Bonds via Cooperative Photoredox and Copper Catalysis DOI

Xu Pin,

Wenzheng Fan, Pinhong Chen

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(30), P. 13468 - 13474

Published: July 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.

Language: Английский

Citations

90
Photoinduced Cobalt-Catalyzed Desymmetrization of Dialdehydes to Access Axial Chirality DOI
Hao Jiang,

Xiang‐Kui He,

Xuan‐Feng Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6944 - 6952

Published: March 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.

Language: Английский

Citations

79
Copper-decorated covalent organic framework as a heterogeneous photocatalyst for phosphorylation of terminal alkynes DOI
Yuxuan Chen, Mo Zhang, Shuai‐Zheng Zhang

et al.

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(10), P. 4071 - 4081

Published: Jan. 1, 2022

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

Language: Английский

Citations

74
Photoinduced copper-catalyzed enantioselective coupling reactions DOI
Liangliang Song, Lingchao Cai, Lei Gong

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(7), P. 2358 - 2376

Published: Jan. 1, 2023

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

Language: Английский

Citations

66
Dynamic Kinetic Reductive Conjugate Addition for Construction of Axial Chirality Enabled by Synergistic Photoredox/Cobalt Catalysis DOI
Wei Xiong, Xuan‐Feng Jiang,

Wencheng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7983 - 7991

Published: March 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.

Language: Английский

Citations

59
Site- and enantioselective cross-coupling of saturated N-heterocycles with carboxylic acids by cooperative Ni/photoredox catalysis DOI Creative Commons
Xiaomin Shu,

De Zhong,

Qian Huang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 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.

Language: Английский

Citations

56
Catalysts driving efficiency and innovation in thermal reactions: A comprehensive review DOI Creative Commons
Wan Nor Roslam Wan Isahak, Ahmed A. Al‐Amiery

Green Technologies and Sustainability, Journal Year: 2024, Volume and Issue: 2(2), P. 100078 - 100078

Published: Feb. 17, 2024

Language: Английский

Citations

30