87372-61-0Relevant articles and documents
Water opens the door to organolithiums and Grignard reagents: Exploring and comparing the reactivity of highly polar organometallic compounds in unconventional reaction media towards the synthesis of tetrahydrofurans
Cicco, Luciana,Sblendorio, Stefania,Mansueto, Rosmara,Perna, Filippo M.,Salomone, Antonio,Florio, Saverio,Capriati, Vito
, p. 1192 - 1199 (2016/02/09)
It has always been a firm conviction of the scientific community that the employment of both anhydrous conditions and water-free reaction media is required for the successful handling of organometallic compounds with highly polarised metal-carbon bonds. Herein, we describe how, under heterogeneous conditions, Grignard and organolithium reagents can smoothly undergo nucleophilic additions to γ-chloroketones, on the way to 2,2-disubstituted tetrahydrofurans, "on water", competitively with protonolysis, under batch conditions, at room temperature and under air. The reactivity of the above organometallic reagents has also been investigated in conventional anhydrous organic solvents and in bio-based eutectic and low melting mixtures for comparison. The scope and limitations of this kind of reaction are discussed.
Multi-product classes obtained from allylation of α-halo ketones with allylzinc bromide
Zhang, Min,Hu, Yuanyuan,Zhang, Songlin
supporting information; experimental part, p. 10732 - 10735 (2010/04/05)
An efficient, one-pot synthesis procedure for the preparation of allylic epoxides, aldehydes and homoallylic alcohols (see scheme) has been described. The three industrial products were synthesized by the reaction of allylzinc bromide with a-halo ketones
Synthesis of Substituted Cyclic Ethers from Halo Ketones and Halo Aldehydes by Palladium-Catalyzed Coupling with Organotin Reagents
Pri-Bar, I.,Pearlman, P. S.,Stille, J. K.
, p. 4629 - 4634 (2007/10/02)
The palladium-catalyzed reaction of a variety of halo ketones or halo aldehydes with acetonyl- and allyltin reagents gives cyclic ethers in good yields.Oxiranes, oxetanes, and tetrahydrofurans can be obtained under mild reaction conditions.The use of palladium catalyst containing chiral monophosphine ligands gave a small enantiomeric excess (up to 19percent) of a chiral oxirane from an α-halo ketone.The allyl- and acetonyloxirane products tend to undergo further transformations in prolonged reactions: allyloxiranes rearrange to α-allyl aldehydes and acetonyloxiranes dehydrate to give substituted furans.The mechanism of the reaction appears to involve addition of the organotin ligand to the carbonyl, followed by palladium(II)-catalyzed cyclization of the tin alkoxides.
