16127-54-1Relevant articles and documents
The First Example of Oxiranyllithium and Oxiranyl Grignard Reagent Having a Carbanion Destabilizing Group: Generation, Property, and Some Synthetic Uses
Satoh, Tsuyoshi,Horiguchi, Kyoko
, p. 8235 - 8238 (1995)
The first generation of destablized oxiranyllithium and oxiranyl Grignard reagent from sulfinyloxiranes with t-BuLi or EtMgCl is described.Treatment of α-methyl α,β-epoxy sulfoxide (sulfinyloxirane) with t-BuLi in THF at -100 deg C gave oxiranyllithium ha
A General Regioselective Synthesis of Alcohols by Cobalt-Catalyzed Hydrogenation of Epoxides
Beller, Matthias,Junge, Kathrin,Leischner, Thomas,Li, Wu,Liu, Weiping
supporting information, p. 11321 - 11324 (2020/05/16)
A straightforward methodology for the synthesis of anti-Markovnikov-type alcohols is presented. By using a specific cobalt triphos complex in the presence of Zn(OTf)2 as an additive, the hydrogenation of epoxides proceeds with high yields and selectivities. The described protocol shows a broad substrate scope, including multi-substituted internal and terminal epoxides, as well as a good functional-group tolerance. Various natural-product derivatives, including steroids, terpenoids, and sesquiterpenoids, gave access to the corresponding alcohols in moderate-to-excellent yields.
A peptide-embedded trifluoromethyl ketone catalyst for enantioselective epoxidation
Romney, David K.,Miller, Scott J.
supporting information; experimental part, p. 1138 - 1141 (2012/05/04)
The development of peptide-based oxidation catalysts that use a transiently generated dioxirane as the chemically active species is reported. The active catalyst is a chiral trifluoromethyl ketone (Tfk) with a pendant carboxylic acid that can be readily incorporated into a peptide. These peptides were capable of epoxidizing alkenes in high yield (up to 89%) and enantiomeric ratios (er) ranging from 69.0:31.0 to 91.0:9.0, depending on the alkene substitution pattern.
Probing competitive enantioselective approach vectors operating in the Jacobsen-Katsuki epoxidation: A kinetic study of methyl-substituted styrenes
Fristrup, Peter,Dideriksen, Brian B.,Tanner, David,Norrby, Per-Ola
, p. 13672 - 13679 (2007/10/03)
This paper describes a study of reactivity and enantioselectivity for a series of methyl-substituted styrenes in the Jacobsen-Katsuki (Mn(salen)-catalyzed) epoxidation reaction. Competition experiments provided kinetic data for the reactivity of the seven possible methyl-substituted styrenes (mono-, di- and trisubstituted) relative to styrene itself, ee values were measured by chiral GC, and absolute configurations were secured by chemical correlation. Of particular interest was the switch in absolute configuration at the benzylic position of the epoxides derived from (Z)- and (E)-α,β-dimethylstyrene, respectively. The results could be rationalized in terms of an approach vector with the phenyl substituent proximal to the salen. As opposed to alkyl groups, a proximal phenyl group has very little effect on the rate of the reaction. Consideration of distal vs proximal approach allows prediction of absolute stereochemistry as a function of alkene substitution pattern. Trisubstituted alkenes with one phenyl group cis to the alkene hydrogen can be identified as a favored substrate class in the title reaction, with both rate and selectivity close to the classic (Z)-β-substituted styrene substrates.
