One‐Pot Synthesis of Homoallylic Ketones from the Addition of Vinyl Grignard Reagent to Carboxylic Esters.

Abstract

Reactions of organo-metal compoundsReactions of organo-metal compounds O 0350 One-Pot Synthesis of Homoallylic Ketones from the Addition of Vinyl Grignard Reagent to Carboxylic Esters. -Optimized reaction conditions allow the preparation of the target compounds without concomitant formation of tertiary alcohol products. -(HANSFORD, K. A.; DETTWILER, J. E.; LUBELL*, W. D.; Org. Lett. 5 (2003) 25, 4887-4890; Dep. Chem., Univ. Montreal, Montreal, Que. H3C 3J7, Can.; Eng.) -Steudel 16-068

Applications of γ,δ-Unsaturated Ketones Synthesized by Copper-Catalyzed Cascade Addition of Vinyl Grignard Reagents to Esters

“…INTRODUCTION γ,δ-Unsaturated ketones (homoallylic ketones) are common intermediates used in the synthesis of natural products, 1 heterocycles, 2 cyclic alkanes, 2,3 therapeutics, 4 and tricyclo[3.2.0]heptanes. 2 Methods to synthesize homoallylic ketones include Carroll and Claisen rearrangements, 5 1,4-conjugate additions onto α,β-unsaturated ketones using various vinyl organometallic reagents, 2 ketone allylations, as well as cross-couplings of olefin and acetylene derivatives onto α,β-unsaturated ketone equivalents using metallo-, 6 and organo-catalysis. 7 These existing routes to homoallylic ketones have however limitations that inhibit broad utility, due in part to requirements for expensive catalysts, toxic reagents and harsh conditions.…”