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Updated: Jun 16, 2025

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Manganese catalyzed chemo-selective synthesis of acyl cyclopentenes: a combined experimental and computational
Koushik Sarkar1, Prativa Behera2, Lisa Roy2
1Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata Mohanpur 741246 West Bengal India bm@iiserkol.ac.in.
Abstract:
Cyclopentenes serve as foundational structures in numerous natural products and pharmaceuticals. Consequently, the pursuit of innovative synthetic approaches to complement existing protocols is of paramount importance. In this context, we present a novel synthesis route for acyl cyclopentenes through a cascade reaction involving an acceptorless-dehydrogenative coupling of cyclopropyl methanol with methyl ketone, followed by a radical-initiated ring expansion rearrangement of the in situ formed vinyl cyclopropenone intermediate. The reaction, catalyzed by an earth-abundant metal complex, occurs under milder conditions, generating water and hydrogen gas as byproducts. Rigorous control experiments and detailed computational studies were conducted to unravel the underlying mechanism. The observed selectivity is explained by entropy-driven alcohol-assisted hydrogen liberation from an Mn-hydride complex, prevailing over the hydrogenation of unsaturated cyclopentenes.
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