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Updated: Jun 9, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Site-Selective Direct γ-Difunctionalization of Diazoenals: Application to the Synthesis of Enal-Functionalized
Jagadeesh Kalepu1, Bapurao Sudam Lad1, Pratap Kumar Mandal1
1Department of Chemistry, Indian Institute of Science Education & Research, 462066, Bhopal, Madhya Pradesh, India.
Abstract:
A new approach for the synthetically important γ-functionalized enals has been developed. The strategy involves rhodium-catalyzed direct C-C & C-S bond forming site-selective γ-difunctionalization of diazoenals with aryl propargyl sulfides via sulfur ylide [2,3] sigmatropic rearrangement, resulting in the highly functionalized γ-allenyl(sulfanyl)enals in excellent yield at ambient temperature. This highly versatile approach constitutes a viable alternative to the remote carbonyl-directed γ-functionalization of unmodified enals which suffer from competitive side reactions. The synthetic utility of the γ-allenyl(sulfanyl)enals was demonstrated by the InCl3-catalyzed cycloisomerization to the trisubstituted furanyl-enals via an unusual 1,4-sulfanyl migration. In addition, an operationally simple and efficient one-pot [3+2] annulation of diazoenals and propargyl sulfides, involving combined γ-difunctionalization and cycloisomerization was successfully developed for the diverse enal-functionalized furans.
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