Issue 45, 2023

Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

Abstract

Enol silyl ethers are versatile, robust, and readily accessible substrates widely used in chemical synthesis. However, the conventional reactivity of these motifs has been limited to classical two electron (2-e) enolate-type chemistry with electrophilic partners or as radical acceptors in one electron (1-e) reactivity leading, in both cases, to exclusive α-monofunctionalization of carbonyls. Herein we describe a mild, fast, and operationally simple one-step protocol that combines readily available fluoroalkyl halides, silyl enol ethers, and, for the first time, hetero(aryl) Grignard reagents to promote selective dicarbofunctionalization of enol silyl ethers. From a broader perspective, this work expands the synthetic utility of enol silyl ethers and establishes bisphosphine–iron catalysis as enabling technology capable of orchestrating selective C–C bond formations with short-lived α-silyloxy radicals with practical implications towards sustainable chemical synthesis.

Graphical abstract: Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

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Article information

Article type
Edge Article
Submitted
29 Aug 2023
Accepted
19 Okt 2023
First published
20 Okt 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 13007-13013

Expanding the chemical space of enol silyl ethers: catalytic dicarbofunctionalization enabled by iron catalysis

D. Sar, S. Yin, J. Grygus, Á. Rentería-Gómez, M. Garcia and O. Gutierrez, Chem. Sci., 2023, 14, 13007 DOI: 10.1039/D3SC04549H

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