Intramolecular Anti-Markovnikov Alkene Hydroaminative Cyclization to cis-2,3-Disubstituted Piperidines DOI

Shaoyu Hao,

Lin Tang, Chaoren Shen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

Multisubstituted piperidines are prevalent units in pharmaceuticals. Herein, a photodriven anti-Markovnikov hydroaminative cyclization of (Z)/(E)-isomeric mixture trisubstituted alkenes using the lactate-derived C2-symmetric arylthiol catalyst was developed for synthesis cis-2,3-disubstituted and azepane high diastereoselectivity good yields. The origin observed different hydroamination rate alkene with configurations were elucidated by experimental computational investigation.

Language: Английский

Enantioselective Decarboxylative Hydrogen-Atom Transfer Reaction DOI

Y.-R. Xu,

Chaoren Shen, Kaiwu Dong

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Direct enantioselective decarboxylative transformations of carboxylic acids have become powerful tools for constructing structurally and functionally diverse molecules. Herein, an unprecedented organocatalyzed protocol enantioconvergent reduction was established by leveraging dual catalysis photoredox-mediated radical generation a thiol-catalyzed asymmetric hydrogen-atom transfer process. With this hydrodecarboxylation, variety chiral 3-substituted indolines were attained from the in moderate to excellent yields with high enantioselectivities.

Language: Английский

Citations

1
Enantioselective Hydrodifluoroalkylation of Alkenes with Conformationally Tuned Peptidyl Hydrogen Atom Transfer Catalysts DOI
Marcus Vinicius Pinto Pereira, Eric P. Geunes, Huiling Shao

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 20, 2025

We report the enantioselective hydrodifluoroalkylation of alkenes proceeding via an asymmetric hydrogen atom transfer (HAT) event catalyzed by thiol-containing tetrapeptides. Photocatalytic generation a difluoroacetyl radical followed carbon–carbon bond formation results in prochiral carbon-centered that engages with chiral catalyst. A trialkylamine reductant is proposed to turn over catalyst this net-reductive transformation. Notably, incorporating (S)-β-methyl-substituted cysteine as N-terminal residue improved selectivity relative native (Cys) residue, and X-ray crystallographic analysis supports conformational underpinning effect. range enantioenriched γ-substituted amides were synthesized up 96:4 enantiomeric ratio, demonstrating broad functional group tolerance method. Models accounting for induction are supporting DFT calculations.

Language: Английский

Citations

0
Reduction of Tertiary Carbon Radicals via Asymmetric Hydrogen Atom Transfer (AHAT)† DOI
Xue Han, Chuan He

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Comprehensive Summary In the past two decades, development of asymmetric radical reactions has achieved tremendous progress, which emerged as a powerful tool for synthesis chiral molecules in synthetic chemistry. Among diverse array processes, transfer hydrogen atoms to tertiary carbon radicals offers potential constructing centers stereoselective fashion. Notwithstanding challenges associated with reactive and evanescent nature species, use reagents or mediators enabled stereocontrol atom ( AHAT ), provides novel avenues advancing field synthesis. Key Scientists

Language: Английский

Citations

1
Catalytic Asymmetric Hydrogen Atom Transfer Based on a Chiral Hydrogen Atom Donor Generated from TBADT and Chiral BINOL DOI
Ling Li, Shiqi Zhang, Xin Cui

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 24, 2024

Enantioselective radical reactions mediated by TBADT have seldom been seen due to the inherent challenges. Herein, we disclose a new chiral hydrogen atom transfer (HAT) reagent that was generated easily from 8

Language: Английский

Citations

1
C 2-Symmetric Chiral Thiol-Catalyzed Hydrogen Atom Transfer for Asymmetric Hydroamination DOI
Benjamin List,

Luc M. Debie

Synfacts, Journal Year: 2024, Volume and Issue: 20(08), P. 0860 - 0860

Published: July 25, 2024

Key words thiol catalysis - photocatalysis radical cations hydrogen atom transfer hydroamination

Language: Английский

Citations

0
Intramolecular Anti-Markovnikov Alkene Hydroaminative Cyclization to cis-2,3-Disubstituted Piperidines DOI

Shaoyu Hao,

Lin Tang, Chaoren Shen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

Multisubstituted piperidines are prevalent units in pharmaceuticals. Herein, a photodriven anti-Markovnikov hydroaminative cyclization of (Z)/(E)-isomeric mixture trisubstituted alkenes using the lactate-derived C2-symmetric arylthiol catalyst was developed for synthesis cis-2,3-disubstituted and azepane high diastereoselectivity good yields. The origin observed different hydroamination rate alkene with configurations were elucidated by experimental computational investigation.

Language: Английский

Citations

0