Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps DOI Creative Commons

Ruijie Mi,

Rong-Kai Wu,

Jierui Jing

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(48)

Published: Nov. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Language: Английский

Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions DOI
Chen‐Xu Liu,

Si‐Yong Yin,

Fangnuo Zhao

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 10079 - 10134

Published: Aug. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Language: Английский

Citations

122
Synthesis of Hexamethyl-1,1′-spirobiindane-Based Chiral Spiro Cp Ligands and Their Application in Rhodium-Catalyzed Enantioselective Aryl C–H Addition to Nitroalkenes DOI
Hui Yang, Ru Zhang,

Suzhen Zhang

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8838 - 8844

Published: June 20, 2023

Spiro cyclopentadienyl rhodium (SCpRh) complexes are powerful catalysts for promoting asymmetric C–H functionalization reactions. However, the application of chiral SCp ligands is limited due to tedious synthetic procedures and expensive starting materials. Herein, we have developed a series spiro (BCSCp) with 6–7 steps from commercially available cheap Bisphenol C. Their corresponding been prepared successfully applied in enantioselective aryl addition nitroalkenes, affording adducts up 88% yield 98% ee.

Language: Английский

Citations

15
Rhodium-catalyzed atroposelective access to trisubstituted olefinsviaC–H bond olefination of diverse arenes DOI Creative Commons
Xiaohan Zhu,

Ruijie Mi,

Jie Yin

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(29), P. 7999 - 8005

Published: Jan. 1, 2023

The atroposelective synthesis of axially chiral acyclic olefins remains a daunting challenge due to their relatively lower racemization barriers, especially for trisubstituted ones. In this work, C-H olefination has been realized open-chain via activation two classes (hetero)arenes in the coupling with sterically hindered alkynes. employment phenyl N-methoxycarbamates as arene reagents afforded phenol-tethered olefins, carbamate being traceless directing group. N-methoxy-2-indolylcarboxamides corresponding olefin by circumventing redox-neutral [4 + 2] annulation. reactions proceeded excellent Z/E selectivity, chemoselectivity, regioselectivity, and enantioselectivity both hydroarylation systems.

Language: Английский

Citations

14
Access to distal biaxial atropisomers by iridium catalyzed asymmetric C–H alkylation DOI Creative Commons
Xueqing Hu,

Yunxu Zhao,

Tong He

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(33), P. 13541 - 13549

Published: Jan. 1, 2024

Herein, we report an iridium-catalyzed asymmetric C–H activation combined with a desymmetrization strategy for synthesizing distal biaxial atropisomers excellent stereoselectivity, displaying promising photophysical and chiroptical properties.

Language: Английский

Citations

4
Synthesis of atropisomers via transition-metal-catalyzed enantioselective carbene transformations DOI
Chongqing Pan, Zhenhua Gu

Trends in Chemistry, Journal Year: 2023, Volume and Issue: 5(9), P. 684 - 696

Published: June 20, 2023

Language: Английский

Citations

9
Quinazolinone-to-Isoquinoline Metamorphosis by Ruthenium-Catalyzed [4+2] Annulation with Sulfoxonium Ylides DOI
Xiaogang Wang, Fei Yuan, Michal Szostak

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(50), P. 10951 - 10957

Published: Dec. 10, 2024

Molecular editing of quinazolinones to isoquinolines by a novel ruthenium-catalyzed [4+2] annulation with sulfoxonium ylides has been developed. The method permits the precise and rapid assembly multisubstituted aminoisoquinolines, class heterocycles that play privileged role in organic synthesis pharmaceutical development. This new catalytic process exhibits programmability, including directed C–H acetylation, nucleophilic cyclization, alcoholysis. Remarkably, various 2-arylquinazolinones could be employed excellent yields broad functional group tolerance. heterocycle-to-heterocycle protocol is compatible green chemistry using an EtOH solvent releasing H2O dimethyl sulfoxide as byproducts.

Language: Английский

Citations

3
Atroposelective Suzuki–Miyaura Coupling Reaction with Benzoxaboroles DOI
Yuqi Cui, Peng Ye,

Yaling Zhang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: June 5, 2025

The asymmetric ring-opening Suzuki-Miyaura cross-coupling (SMC) reaction of ortho-disubstituted aryl bromides with cyclic benzoxaboroles has been developed for the first time by using a commercially available Et-AntPhos as chiral ligand, offering general access to diverse axial biaryl benzyl alcohols in high enantioselectivity (up 97:3 er). This protocol also features mild conditions and broad substrate scope, demonstrating potential transformations.

Language: Английский

Citations

0
Rhodium(I)‐Catalyzed Asymmetric Hydroarylative Cyclization of 1,6‐Diynes to Access Atropisomerically Labile Chiral Dienes DOI
Panjie Hu,

Lingfei Hu,

Xiao‐Xi Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 16, 2023

Abstract Axially chiral open‐chained olefins are an underexplored class of atropisomers, whose enantioselective synthesis represents a daunting challenge due to their relatively low racemization barrier. We herein report rhodium(I)‐catalyzed hydroarylative cyclization 1,6‐diynes with three distinct classes arenes, enabling highly broad range axially 1,3‐dienes that conformationally labile (Δ G ≠ ( rac )=26.6–28.0 kcal/mol). The coupling reactions in each category proceeded excellent enantioselectivity, regioselectivity, and Z/E selectivity under mild reaction conditions. Computational studies the quinoline N ‐oxide system reveal proceeds via initial oxidative 1,6‐diyne give rhodacyclic intermediate, followed by σ‐bond metathesis between arene C−H bond Rh−C(vinyl) bond, subsequent C−C reductive elimination being enantio‐determining turnover‐limiting. DFT‐established mechanism is consistent experimental studies. coupled products ‐oxides undergo facile visible light‐induced intramolecular oxygen‐atom transfer, affording epoxides complete axial‐to‐central chirality transfer.

Language: Английский

Citations

8
Rhodium-catalyzed enantioselective annulation of N-phenoxyacetamides with 1,3-dienes DOI
Hui Yang, Ziqi Yang,

Suzhen Zhang

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(10), P. 2842 - 2846

Published: June 6, 2023

Language: Английский

Citations

6
Synthesis of Spirocyclohexadienones via Palladium-Catalyzed Dearomatization of Dibenzoxaborins DOI

Yuyao Zhao,

Lincong Sun,

Junbiao Chang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1056 - 1061

Published: Jan. 29, 2024

The development of Pd(II)-catalyzed dearomatization transformation dibenzoxaborins with alkynes triggered by transmetalation from boron to palladium has been achieved, leading the synthesis spirocyclohexadienones, an important skeleton demonstrating potential biomedical utility. [3 + 2] spiroannulation exhibits remarkable regioselectivity and broad substrate scope under mild reaction conditions. This methodology employs dibenzoxaborin as a establish formal 2-phenylphenol, which poses formidable energy barrier destruction aromaticity.

Language: Английский

Citations

2