95249-25-5Relevant academic research and scientific papers
Stereoselective Traceless Borylation–Allenation of Propargylic Epoxides: Dual Role of the Copper Catalyst
Jarava-Barrera, Carlos,Parra, Alejandro,Amenós, Laura,Arroyo, Ana,Tortosa, Mariola
supporting information, p. 17478 - 17481 (2017/11/30)
Chiral α-allenols are prepared with high diastereocontrol through an unprecedented and spontaneous β-oxygen elimination of an α-epoxy vinyl boronate. Stochiometric experiments and DFT calculations support a dual role of the copper catalyst, which orchestrates the hydroboration and the syn-elimination step.
An alternative reaction outcome in the gold-catalyzed rearrangement of 1-alkynyloxiranes
Gonzalez, Maria J.,Gonzalez, Jesus,Vicente, Ruben
supporting information, p. 6140 - 6143,4 (2020/09/16)
The gold(III)-catalyzed rearrangement of tetrasubstituted 1-alkynyloxiranes is described. This transformation led to a different reaction outcome with respect to related substrates previously studied. Thus, tertiary α-alkynylketones or alkynols can be selectively obtained. Moreover, gold(III) proved capable to catalyze the rearrangement of simple epoxides. These results indicate that gold(III) complexes act as oxophilic Lewis acids rather than π-acids in these transformations.
Dual role of alkynyl halides in one-step synthesis of alkynyl epoxides
Trofimov, Alexander,Chernyak, Natalia,Gevorgyan, Vladimir
supporting information; experimental part, p. 13538 - 13539 (2009/02/06)
It was demonstrated that alkynyl halides could serve as a source of Br+ and acetylide ions in the same transformation. This allowed for the efficient one-step preparation of alkynyl epoxides, important organic building blocks, from readily available starting materials. Copyright
Reaction ofα- Halo Ketones with Nucleophiles
Russell, Glen A.,Ros, Fransisco
, p. 2506 - 2511 (2007/10/02)
p-Nitro- or p-cyanophenacyl chloride or the 1,1-dimethyl derivatives react with the anion of 2-nitropropane to form the C-alkilation product by a radical chain mechanism (SRN1).With the 1,1-dimethyl derivatives, the free radical substitution is photostimulated and occurs in competition with ionic reactions leading to the oxiranes 5 and hydroxy ketones 6.When K+ is used as the counterion, the SRN1 process is favored by complexation with 18-crown-6. p-Nitro-1,1-dimethylphenacyl chloride gives substitution products with diethyl malonate or diethyl mthylmalonate anions via the SRN1 process, but with PhS- or p-MeC6H4SO2-, substitution occurs by competing ionic and radical processes.Propylacetylenide anion reacts to form the oxirane 13a while diethyl phosphite or thiophosphite anions yield the enol phosphate 14a or thiophosphate 14b. 1,1-Dimethylphenacyl chloride reacts by nonradical processes to give the oxirane with acetylenide anions, the substitution products with PhS- or p-MeC6H4SO2- and a mixture of the enol phosphate, and oxirane 16 with diethyl phosphite anion.With Me2C==NO2-K+, mainly the oxirane is formed in Me2SO but mainly substitution via the SRN1 chain is observed in HMPA.
