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Copper‐Catalyzed Ring‐Expansion/Thiolactonization via Azidation of Internal Olefinic C–H Bond under Mild Conditions
Author(s) -
Guo Tenglong,
Jiang Quanbin,
Yu Zhengkun
Publication year - 2016
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201600675
Subject(s) - chemistry , amination , acetic anhydride , phenylacetylene , ring (chemistry) , medicinal chemistry , catalysis , ketene , organic chemistry , sodium azide , polymer chemistry
A copper(I)‐catalyzed, (diacetoxyiodo)benzene [PhI(OAc) 2 ]‐mediated ring‐expansion/thiolactonization of α‐oxo ketene dithioacetals was efficiently realized via azidation of the internal olefinic C−H bond with sodium azide under mild conditions. Sequential amination, ring‐expansion rearrangement, and thiolactonization occurred to form aminated thiolactones in the presence of acetic anhydride as the additive, while only C−H amination to afford the unprotected enamines occurred when using ammonium sulfide as a reducing additive. The in situ generated vinyl azides were confirmed as the reactive intermediates, which were captured by phenylacetylene to produce triazoles. This protocol provides a concise route to thiolactone derivatives and unprotected enamines.