Organocatalytic Atroposelective Cross‐Coupling of 1‐Azonaphthalenes and 2‐Naphthols DOI

Bing‐Chao Da,

Yong‐Bin Wang, Jun Kee Cheng

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: April 26, 2023

Atroposelective cross-coupling is one of the most appealing routes to construct axially chiral binaphthyl molecules due modular and succinct nature. Although transition-metal-catalyzed cross-couplings offer reliable synthetic means, alternative reaction modes that could be applied broader substrate range without their pre-functionalization highly desirable. Herein we show application Brønsted acid catalyst as organocatalyst accomplish 1-azonaphthalenes 2-naphthols with high efficiency, exclusive C4-selectivity well excellent enantioselectivity functional group compatibility. The identification acylimidazolinone auxiliary for azo activating group, effective remote control arene resonance effect synergistically play key roles in development this method. utility further demonstrated by transformations products into other compounds perfectly retained axial chirality.

Language: Английский

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

82

Catalytic atroposelective synthesis DOI
Shao‐Hua Xiang, Wei‐Yi Ding, Yong‐Bin Wang

et al.

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

Citations

38

Atroposelective catalysis DOI

Tanno A. Schmidt,

Valeriia Hutskalova,

Christof Sparr

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 497 - 517

Published: June 18, 2024

Language: Английский

Citations

21

Beyond conventional: Role of chiral metal–organic frameworks in asymmetric scenarios DOI

Maryam Chafiq,

Abdelkarim Chaouiki, Jungho Ryu

et al.

Nano Today, Journal Year: 2024, Volume and Issue: 56, P. 102227 - 102227

Published: March 18, 2024

Language: Английский

Citations

19

An Enantioselective Suzuki–Miyaura Coupling To Form Axially Chiral Biphenols DOI Creative Commons

Robert Pearce-Higgins,

Larissa N. Hogenhout,

Philip J. Docherty

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 15026 - 15032

Published: Aug. 15, 2022

Axial chirality features prominently in molecules of biological interest as well chiral catalyst designs, and atropisomeric 2,2′-biphenols are particularly prevalent. Atroposelective metal-catalyzed cross-coupling is an attractive modular approach to access enantioenriched biphenols, yet existing protocols cannot achieve this directly. We address challenge through the use enantiopure, sulfonated SPhos (sSPhos), ligand that has until now been used only racemic form derives its from axis introduced sulfonation. believe noncovalent interactions involving sulfonate group responsible for high levels asymmetric induction we obtain 2,2′-biphenol products Suzuki–Miyaura coupling, have developed a highly practical resolution sSPhos via diastereomeric salt recrystallization.

Language: Английский

Citations

45

Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes DOI
Pu‐Fan Qian, Tao Zhou, Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Language: Английский

Citations

43

Desymmetrization of Vicinal Bis(boronic) Esters by Enantioselective Suzuki–Miyaura Cross-Coupling Reaction DOI
Mingkai Zhang, Paul S. Lee, Christophe Allais

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8308 - 8313

Published: April 6, 2023

The development of an enantioselective catalytic Suzuki-Miyaura reaction that applies to

Language: Английский

Citations

30

Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Language: Английский

Citations

18

Modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs DOI
Li‐Qing Ren, Baoquan Zhan,

Jiayi Zhao

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 83 - 91

Published: Sept. 20, 2024

Language: Английский

Citations

14

Enantioselective Rhodium‐Catalyzed C−H Arylation Enables Direct Synthesis of Atropisomeric Phosphines DOI
Zexian Li,

Weipeng Xu,

Shuaishuai Song

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 6, 2024

Atropisomeric phosphines hold considerable significance in asymmetric catalysis, yet their synthesis presents a formidable challenge owing to intricate multistep procedures. In this context, groundbreaking methodology has been presented for preparation. This innovative approach entails an atroposelective rhodium-catalyzed C-H activation employing aryl and heteroaryl halides, chelated by P(III) center. The essence of strategy lies its ability directly construct chiral phosphine ligands single step, thereby exhibiting exceptional efficiency terms atom redox economy. Illustrative examples serve demonstrate the immense potential situ-formed catalysis. Mechanistic experiments have further provided invaluable insights into transformation.

Language: Английский

Citations

11