Catalyst‐Free Regioselective Diborylation of Aryllithium with Tetra(o‐tolyl)diborane(4) DOI Creative Commons
Xiaofeng Mao, Zhenpin Lu, Jie Zhang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(6)

Published: Dec. 21, 2023

Abstract A catalyst‐free 1,2‐diborylation of aryllithium with tetra( o ‐tolyl)diborane(4) has been achieved, giving a series 1,2‐diborylaryl lithium species in excellent yields under mild reaction conditions, which leads to 1,2‐di(tolyl)borylarenes 60–91 % upon treatment the hydride‐abstracting reagent. In these transformations, one sp 2 C−H arene is activated and both boryl units are utilized build two new (sp )C−B bonds. This represents strategy for selective diborylation. Density functional theory (DFT) calculations suggest that an aromatic nucleophilic substitution key step formation products.

Language: Английский

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

32
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

16
Atroposelective Synthesis of Diarylamines via Organocatalyzed Electrophilic Amination DOI

Zidan Ye,

Wansen Xie,

Donglei Wang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4958 - 4967

Published: March 18, 2024

Axially chiral diarylamine atropisomers represent a distinct category characterized by two contiguous C–N axes, which exhibit significantly lower racemization barrier due to the concerted rotation of both axes. In this work, we introduce an effective method for atroposelective synthesis axially diarylamines through organocatalyzed asymmetric electrophilic amination with azodicarboxylates, afforded variety acyclic secondary in good yields high enantioselectivities. This expands scope catalytic beyond N-aryl quinoid-type atropisomers, enabling without constraining one axis intramolecular hydrogen bonding. Both experimental and computational studies show minimal contribution bonding stabilizing configurations these undergo via

Language: Английский

Citations

12
N‐Heterocycle‐Editing to Access Fused‐BN‐Heterocycles via Ring‐Opening/C−H Borylation/Reductive C−B Bond Formation DOI
Xu Zhang,

Wanlan Su,

Huosheng Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 10, 2024

Skeletal editing of N-heterocycles has recently received considerable attention, and the introduction boron atom into heterocycles often results in positive property changes. However, direct enlargement through insertion is rarely reported literature. Here, we report a N-heterocyclic reaction combination C-H borylation, accessing fused-BN-heterocycles. The synthetic potential this chemistry was demonstrated by substrate scope late-stage diversification products.

Language: Английский

Citations

10
Atroposelective Construction of Carbon–Boron Axial Chirality through Rh-Catalyzed [2 + 2 + 2] Cycloaddition DOI
Yifan Ping, Xiaofan Shi, Ming Lei

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5064 - 5076

Published: March 20, 2024

Axially chiral compounds have widespread applications in many fields. While significant progress has been made for the asymmetric synthesis of atropisomers consisting C–C bonds, an efficient approach construction C–B is still lacking. Herein, we report a practical method atroposelective axially arylboron through Rh-catalyzed [2 + 2 2] cycloaddition. The reaction exhibits broad substrate scope and good functional group tolerance, thus providing protocol to access variety high yields enantiocontrol. utility these adequately demonstrated by versatile transformations into highly valuable such as phosphine ligands fluorescent molecules. Mechanistic experiments DFT calculations provided insights mechanism well origin

Language: Английский

Citations

9
Dynamic kinetic resolution and dynamic kinetic asymmetric transformation of atropisomeric biaryls DOI
Jie Zhang,

Xuan-Zhu Huo,

Yidan Liu

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101329 - 101329

Published: March 1, 2025

Language: Английский

Citations

1
Enantioselective Synthesis of “NO2···NH” Hydrogen Bond-Stabilized C–N Axially Chiral Diarylamines DOI
Wei Lin,

Yingbo Shao,

Zeyang Hao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(2), P. 1183 - 1192

Published: Jan. 9, 2024

Herein, N-nucleophilic tandem oxidation–N-arylation–oxidation reaction and C-nucleophilic bromination of substituted anilines have been developed using chiral phosphoric acid catalysis, enabling access to axially diarylamines. The key feature this strategy is that the "NO2···H–N" hydrogen bond was successfully introduced into acyclic diaryl secondary amines, which contain two potential contiguous atropisomeric C–N axes, stabilize one planar axial conformations. This methodology provided a series optically pure diarylamine atropisomers containing new type in good yields (up 99%) high enantiomeric ratios 99.5:0.5 e.r.). synthetic utility demonstrated through large-scale reactions transformations products. Plausible models were proposed explain enantioselectivity

Language: Английский

Citations

7
Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction DOI

Shi-Jiang He,

Boming Shen,

Lian-Zheng Zuo

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 19137 - 19145

Published: July 2, 2024

Anthracenylidene is an intriguing structural unit with potential in various fields. The study presents a novel approach to introducing axial chirality into this all-carbon core skeleton through remotely controlled desymmetrization strategy. A palladium-catalyzed enantioselective Heck arylation of exocyclic double bond anthracene two distinct substituents at the C10 position harnessed realize such transformation. judicious identification P-centrally chiral ligand pivotal ensure competitive competence reactivity and stereocontrol when heteroatom handle absent from anthracenylidene skeleton. Both mono- disubstituted substrates were compatible for established catalytic system, structurally diverse anthracenylidene-based frameworks forged good-to-high enantiocontrol. subsequent derivatization obtained products yielded valuable array centrally axially molecules, thus emphasizing practicality chemistry. DFT calculations shed light on mechanism provided insights origin experimentally observed enantioselectivity reaction.

Language: Английский

Citations

7
Copper-catalysed asymmetric annulation of yne-allylic esters with amines to access axially chiral arylpyrroles DOI Creative Commons

Chaochao Yao,

Danran Li,

Hua-Ming Xiang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 10, 2024

The construction of atropisomers with 1,2-diaxes, while maintaining high enantiocontrol, presents a significant challenge due to the dynamic nature steric hindrance at ortho-aryl substituents. Although various catalytic asymmetric methods have been developed for accessing axially chiral arylpyrroles, synthesis arylpyrroles 1,2-diaxes in manner has remained rare. Herein, authors report diverse and C-C C-N axes through copper-catalysed asymmetirc [4 + 1] annulation yne-allylic esters arylamines via remote stereocontrol strategy. This approach provides facile access broad range heterobiaryl (67 examples) excellent enantioselectivities, each bearing one or two C-C/C-N axes, demonstrating its versatility efficiency. utility this methodology is further highlighted by transformation product into phosphine ligand, thioureas use catalysis.

Language: Английский

Citations

6
Palladium‐Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality DOI Open Access
Jie Xu, Weihua Qiu, Xu Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 16, 2023

Abstract The direct C−H functionalization of 1,2‐benzazaborines, especially asymmetric version, remains a great challenge. Here we report palladium‐catalyzed enantioselective olefination and allylation reactions 1,2‐benzazaborines. This approach is kinetic resolution (KR), providing various C−B axially chiral 2‐aryl‐1,2‐benzazaborines 3‐substituted in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). synthetic potential this reaction showcased by late‐stage modification complex molecules, scale‐up reaction, applications.

Language: Английский

Citations

16