Spiro-Annulation of Ene-diones with Iodonium Ylides: An Anomalous Cloke-Wilson Rearrangement for the Regioselective
Basit Qayoom1, Auqib Rashid1,2,3, Gowhar Ahmad Rather1,3
1Natural Products & Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine (IIIM), Jammu, Jammu and Kashmir 180001, India.
Abstract:
An efficient synthesis of spirodihydrobenzofuran derivatives via the 1,4-conjugate addition of iodonium ylides to indene-1,3(2H)-diones, followed by an anomalous Cloke-Wilson rearrangement is reported. This strategy demonstrates a broad substrate scope with a high degree of regioselectivity control. Computational studies involving the natural orbital bond analysis were explored to explain this anomalous formation of unconventional products. In case of alkyne-tethered indenediones, the same regioselectivity control was observed, but in the presence of scandium-triflate in dimethoxyethane (DME), the normal Cloke-Wilson product was observed as an exclusive product.
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