Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals DOI Creative Commons

Jun-Bin Tang,

Jun-Qian Bian,

Zhihan Zhang

et al.

Published: June 8, 2023

Enantioselective intermolecular atom transfer reactions of vinyl radicals have hitherto remained elusive mainly due to their inherently high instability and reactivity which significantly compromises the stereodiscriminating substrate-catalyst interactions. Herein, we describe Cu(I)-catalyzed enantioselective chlorine with using tailormade tridentate anionic N,N,N-ligands featuring bulky peripheral substituents. This reaction readily accommodates (hetero)aryl alkyl sulfonyl chlorides as radical precursors more importantly, a large panel 2-aminoaryl 2-oxyaryl alkynes substrates, providing highly transformable axially chiral in moderate good yield excellent enantioselectivity. The can be easily scaled up gram scales straightforward manipulations thus obtained halides lead thiourea, pyridyl carboxamide, quinolyl sulfonamide compounds, are promising reagents for asymmetric catalysis. Both experimental theoretical mechanistic studies supported proposed mechanism.

Language: Английский

Rhodium‐Catalyzed Chemo‐, Regio‐, Diastereo‐, and Enantioselective Intermolecular [2+2+2] Cycloaddition of Three Unsymmetric 2π Components DOI Creative Commons

Ryota Shimotsukue,

Kohei Fujii,

Yu Sato

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 16, 2023

We have developed the Rh+ /H8 -binap-catalyzed chemo-, regio-, diastereo-, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis-enamide to yield protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene silylacetylene enables distinct These transformations proceed excellent selectivity (complete regio- diastereoselectivity up >99 % ee). Mechanistic studies suggest chemo- regioselective formation rhodacyclopentadiene intermediate from terminal alkynes.

Language: Английский

Citations

15
Chiral Boro‐Phosphate Catalyzed Asymmetric Transfer Hydrogenation of 1‐Enal Substituted 2‐Naphthols: Access to Axially Chiral Styrene‐Type Allylalcohols DOI

Hong‐Xin Jiang,

Dandan Han,

Rui‐Ping Song

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(9), P. 1398 - 1404

Published: April 12, 2023

Abstract Herein, we present a chiral boro‐phosphate catalyzed atroposelective asymmetric transfer hydrogenation method, leading to family of axially styrene‐type allylalcohols. This dynamic kinetic resolution approach portrays simple procedure, mild conditions and good enantiocontrol (51–95% ee), thus providing an important alternative assemble the challenging atropisomeric aryl‐acyclic alkene scaffolds. magnified image

Language: Английский

Citations

5
Organocatalytic Atroposelective Hydrochalcogenation of Alkynes to Access Axially Chiral Vinyl Chalcogenides DOI Creative Commons

Yi-Xin Wang,

Jing-Run Wang,

Chen Cui

et al.

Published: Aug. 16, 2024

The low racemization barrier inherent in axially chiral vinyl sulfides/selenides (G ≤ 26.8 kcal/mol) poses a significant challenge for achieving atroposelective hydrochalcogenation of alkynes. In this study, we present an unprecedented alkynes catalyzed by organocatalysts. This organocatalytic, atom-economic process proceeds under mild conditions and exhibits exceptional enantio-, regio-, E-stereoselectivity. Insights from detailed Density Functional Theory (DFT) studies elucidate the origins these high selectivities.

Language: Английский

Citations

1
Rhodium‐Catalyzed Chemo‐, Regio‐, Diastereo‐, and Enantioselective Intermolecular [2+2+2] Cycloaddition of Three Unsymmetric 2π Components DOI Creative Commons

Ryota Shimotsukue,

Kohei Fujii,

Yu Sato

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(16)

Published: Feb. 16, 2023

Abstract We have developed the Rh + /H 8 ‐binap‐catalyzed chemo‐, regio‐, diastereo‐, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis ‐enamide to yield protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene silylacetylene enables distinct These transformations proceed excellent selectivity (complete regio‐ diastereoselectivity up >99 % ee ). Mechanistic studies suggest chemo‐ regioselective formation rhodacyclopentadiene intermediate from terminal alkynes.

Language: Английский

Citations

2
Cu(I)-catalysed enantioselective chlorine atom transfer with vinyl radicals DOI Creative Commons

Jun-Bin Tang,

Jun-Qian Bian,

Zhihan Zhang

et al.

Published: June 8, 2023

Enantioselective intermolecular atom transfer reactions of vinyl radicals have hitherto remained elusive mainly due to their inherently high instability and reactivity which significantly compromises the stereodiscriminating substrate-catalyst interactions. Herein, we describe Cu(I)-catalyzed enantioselective chlorine with using tailormade tridentate anionic N,N,N-ligands featuring bulky peripheral substituents. This reaction readily accommodates (hetero)aryl alkyl sulfonyl chlorides as radical precursors more importantly, a large panel 2-aminoaryl 2-oxyaryl alkynes substrates, providing highly transformable axially chiral in moderate good yield excellent enantioselectivity. The can be easily scaled up gram scales straightforward manipulations thus obtained halides lead thiourea, pyridyl carboxamide, quinolyl sulfonamide compounds, are promising reagents for asymmetric catalysis. Both experimental theoretical mechanistic studies supported proposed mechanism.

Language: Английский

Citations

1