Copper-Catalyzed Ring-Expansion/Thiolactonization via Azidation of Internal Olefinic C-H Bond under Mild Conditions

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...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2016-11, Vol.358 (21), p.3450-3457
Main Authors: Guo, Tenglong, Jiang, Quanbin, Yu, Zhengkun
Format: Article
Language:English
Subjects:
Additives
Ammonium sulfides
Anhydrides
Bonding
copper
C−H functionalization
Derivatives
enamines
internal olefins
Ketenes
Sodium azides
thiolactones
Triazoles
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Summary: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.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201600675