Asymmetric Radical-Type Clayden Rearrangement for the Synthesis of Enantiopure 1,2-Aminothiols and 1,2-Aminoalcohols.
- 1State Key Laboratory of Analytical Chemistry for Life Sciences, School of Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), ChemBioMed Interdisciplinary Research Center at Nanjing University, Nanjing University, Nanjing 210023, P. R. China.
- 2Shanghai Frontiers Science Center of Drug Target Identification and Delivery, National Key Laboratory of Innovative Immunotherapy, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Pharmaceutical Sciences, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Abstract
We report herein an expedient method for the construction of enantiopure 1,2-aminothiols and 1,2-aminoalcohols starting from polar amino acids cysteine and serine via a photoredox-catalyzed, decarboxylation-enabled asymmetric radical-type Clayden rearrangement. The strategy of "self-regeneration of stereocenters (SRS)" is employed to enable the stereoselective 1,4-N-to-C radical aryl migration of heterocyclic ureas, which serve as rigid-scaffold substrates and can be readily derived from serine and cysteine. A wide range of migrating groups, including multisubstituted and heterocyclic aryls, are well tolerated and afford the aryl migration products with excellent diastereoselectivity. This strategy not only offers a practical route to enantiopure 1,2-aminothiols and 1,2-aminoalcohols but also paves a new way for asymmetric radical Truce-Smiles rearrangement, holding great potential for the construction of aryl-containing chiral building blocks.
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BibTeX
@article{jiang2026asymmetric,
title = {{Asymmetric Radical-Type Clayden Rearrangement for the Synthesis of Enantiopure 1,2-Aminothiols and 1,2-Aminoalcohols.}},
author = {Sen Jiang and Jie Xu and Meng-Yao Zhang and Yan Zhang and Heng Jiang},
journal = {JACS Au},
year = {2026},
month = sep,
doi = {10.1021/jacsau.6c01132},
url = {https://europepmc.org/article/MED/42953199},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Asymmetric Radical-Type Clayden Rearrangement for the Synthesis of Enantiopure 1,2-Aminothiols and 1,2-Aminoalcohols.
AU - Sen Jiang
AU - Jie Xu
AU - Meng-Yao Zhang
AU - Yan Zhang
AU - Heng Jiang
PY - 2026
DA - 2026/09/21
JO - JACS Au
DO - 10.1021/jacsau.6c01132
UR - https://europepmc.org/article/MED/42953199
AB - We report herein an expedient method for the construction of enantiopure 1,2-aminothiols and 1,2-aminoalcohols starting from polar amino acids cysteine and serine via a photoredox-catalyzed, decarboxylation-enabled asymmetric radical-type Clayden rearrangement. The strategy of "self-regeneration of stereocenters (SRS)" is employed to enable the stereoselective 1,4-N-to-C radical aryl migration of heterocyclic ureas, which serve as rigid-scaffold substrates and can be readily derived from serine and cysteine. A wide range of migrating groups, including multisubstituted and heterocyclic aryls, are well tolerated and afford the aryl migration products with excellent diastereoselectivity. This strategy not only offers a practical route to enantiopure 1,2-aminothiols and 1,2-aminoalcohols but also paves a new way for asymmetric radical Truce-Smiles rearrangement, holding great potential for the construction of aryl-containing chiral building blocks.
SN - 2691-3704
ER -