The Nucleophile Intercepted Meyer-Schuster Rearrangement of the (Z-enoate and Z-enal) Propargylic Alcohols

The classical Meyer–Schuster rearrangement (MSR) of propargylic alcohols to -enones is a century old transformation. However, its electrophile intercepted version is a recent modification for the synthesis of -functionalized enones. During the last decade (2015-2025) our research group at IIT Madras had developed a nucleophile intercepted version of the classical Mayer-Schuster rearrangement by employing the Z-enoate as well as Z-enal assisted propargylic alcohols. In this account we have detailed the design, discovery and development of this novel and robust synthetic process. This modification of classical MSR has emerged as a powerful tool for the synthesis of highly functionalized -enones, and structurally unique polycyclic frameworks such as butenolide fused allenes and butenolide based atropisomeric compounds, naphthofurans, benzofurans, 2-vinylfurans, 2-acylfurans and carbazoles. This reaction strategy was further utilized for the partial as well as total synthesis of several natural products, such as amycofuran, & frondosin B and carbazoquinocins, lipocarbazoles, carazostatin, rubrolides respectively. Several fruitful control experiments and isolation of the relevant intermediates helped us to understand the possible mechanistic pathway for this process. We hope that this modified version of the MSR will be further expanded in forthcoming future.

Publication History

Received: 01 September 2025

Accepted after revision: 08 October 2025

Accepted Manuscript online:
08 October 2025