Nanjing University Shi Zhuangzhi Team's Research on ACS Cent. Sci. – Novel Applications of Josiphos
Created on 09.25
Nanjing University Shi Zhuangzhi Team's Research onACS Cent. Sci. – Novel Applications of Josiphos
The team led by Prof. Zhuangzhi Shi from Nanjing University reports abreakthrough in ACS Central Science: Copper-Catalyzed Asymmetric CyclizativeSulfinamidation: Forging Indole-Based Stereogenic Sulfur(IV) Centers andAtropisomeric Chirality. This work addresses the underexplored chemical spaceof chiral S(IV)-containing sulfinamides, which are critical intermediates indrug design due to their balanced stability and reactivity. By employing Josiphosas a key ligand, the team achieves enantioselective synthesis of indolesulfinamides with exceptional selectivity and functional group tolerance.
ReactionOptimization
Substrate Scope
Key Advantages of Josiphos Ligand：
1、Superior Enantiocontrol:
Josiphos dramatically enhances enantioselectivity,increasing product ee from 17–26% (with other ligands) to 92–95% afteroptimization.
2、Broad Substrate Compatibility:
The CuBr-Josiphos system stabilizes active catalytic species, accommodatingdiverse o-alkynylanilines with alkyl, aryl, heterocyclic, halogen,ether, or ester groups while maintaining high stereoselectivity.
3、Facile Post-Functionalization:
Products generated via Josiphos catalysis undergo efficient transformations,and all transformations preserve high enantioselectivity anddiastereoselectivity:
l Deprotection with methanesulfonic acid → Primary
sulfinamides
l Reaction with trichloroisocyanuric acid → Sulfonyl
imidoyl chlorides
l Halogen-magnesium exchange/Sonogashira coupling →
Allylated/cyanated derivatives
Literature details
Authors：Xiaowu Fang,#Fengrui Xiang,# Yue Zhao, and Zhuangzhi Shi*
Title: Copper-Catalyzed Asymmetric CyclizativeSulfinamidation: Forging Indole-Based Stereogenic Sulfur(IV) Centers andAtropisomeric Chirality
DOI：10.1021/acscentsci.5c00909