56246-59-4Relevant articles and documents
Stereo- and regioselectivity in the P450-catalyzed oxidative tandem difunctionalization of 1-methylcyclohexene
Roiban, Gheorghe-Doru,Agudo, Rubén,Reetz, Manfred T.
, p. 5306 - 5311 (2013/07/05)
The selective partial oxidation of small non-functionalized molecules using biocatalysis based on P450 monooxygenases is known to be difficult due to the expected poor regio- and stereoselectivity, but in this study it was nevertheless attempted. 1-Methyl
Epoxidation process using amine catalysts
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Page/Page column 5, (2008/06/13)
A process for the epoxidation of an alkene, which process comprises reaction of an alkene with an oxidising agent in the presence of a catalyst, characterised in that the catalyst is an amine of formula (I), wherein T represents hydrogen or a moiety of formula (a); R1, R2, R3, R4, R5 and R6 each independently represents hydrogen, optionally substituted alkyl, an optionally substituted aryl group, heterocyclyl or an optionally substituted aralkyl group wherein substituents for the above mentioned groups are selected from up to three of alkyl, aryl, heterocycyl, hydroxy, alkoxy or a group NRsRt wherein R5 and Rt each independently represents hydrogen, alkyl or alkylcarbonyl and R7 represents hydrogen, alkyl, aryl or aralkyl; or T represents a moiety (a) wherein R1 together with R2 represents an optionally substituted alkylene chain comprising 2 to 6 carbon atoms the alkylene chain being optionally interrupted with an oxygen atom or a group NRp wherein Rp is hydrogen or alkyl, and wherein optional substituents for any carbon atom of the alkylene chain are selected from hydroxy, alkoxy, oxo or a group NRsRt wherein Rs and Rt each independently represents hydrogen, alkyl or alkylcarbonyl or substituents on any two adjacent carbon atoms of the chain together with the carbon atoms to which they are attached form an alicyclic, aryl or heterocyclic ring; and R3, R4, R5, R6 and R7 are as defined above.
Allylic alcohols via catalytic asymmetric epoxide rearrangement
Soedergren, Mikael J.,Bertilsson, Sophie K.,Andersson, Pher G.
, p. 6610 - 6618 (2007/10/03)
Epoxides using chiral lithium amides, but other than for a small subset of meso-epoxides, insufficient reactivity and enantioselectivity hamper the existing methods. Furthermore, the chiral reagents are often required in large excess. This study presents a general and highly enantioselective process that, in addition, is based on catalytic amounts (5 mol %) of enantiopure (1S,3R,4R)-3-(1-pyrrolidinyl)methyl-2-azabicyclo[2.2.1]heptane and lithium diisopropylamide as the stoichiometric base. The influence of structural modification of the catalyst is studied in terms of activity, enantioselectivity, and aggregation behavior. The utility of the process is demonstrated by its application to a variety of epoxide derivatives (≥94% ee for 11 out of 14 examples), including the formal syntheses of, e.g., a prostaglandin core unit, epibatidine, carbovir, faranal, and lasiol. The system is readily extended to the resolution of racemic epoxides, which allows access to highly enantioenriched epoxides or allylic alcohols, even at conversions near 50%.
