94458-92-1Relevant articles and documents
Improvement of a stereoselective biocatalytic synthesis by substrate and enzyme engineering: 2-hydroxy-(4×-oxocyclohexyl)acetonitrile as the model
Avi, Manuela,Wiedner, Romana M.,Griengl, Herfried,Schwab, Helmut
experimental part, p. 11415 - 11422 (2009/10/17)
Even if biocatalysis is finding increasing application, it still has to gain widespread use in synthetic chemistry. Reasons for this are limitations that enzymes have with regard to substrate range, reaction scope, and insufficient selectivity with unnatural compounds. These shortcomings can be challenged by enzyme and/or substrate engineering, which are employed to alter substrate specificity and enhance the enzyme selectivity toward unnatural substrates. Herein, these two approaches are coupled to improve the hydroxynitrile lyase catalyzed synthesis of 2-hydroxy-(4′-oxocyclohexyl) acetonitrile (4). The ketone functionality is masked as an enol ether, and the oxynitrilase of Hevea brasiliensis is engineered towards this masked substrate to give the product with a high optical purity and to drastically lower the amount of enzyme needed.
1,3-Benzodithiolium Cation Mediated Cyclization Reactions
Rigby, James H.,Kotnis, Atul,Kramer, James
, p. 5078 - 5088 (2007/10/02)
General protocols for the construction of various ring systems employing cation olefin cyclizations initiated by the readily accessible 1,3-benzodithiolium ion are described.Several substituted tetralones and tetralins can be rapidly assembled by this methodology as can a variety of substituted bicyclooctane and tricyclic ring systems.The products of these transformations are amenable to interconversion into a range of functionalized species.
SYNTHESIS OF BICYCLOOCTANES BY A TANDEM DIELS-ALDER-CARBOCATION CYCLIZATION STRATEGY
Rigby, James H.,Kotnis, Atul S.
, p. 4943 - 4946 (2007/10/02)
The bicyclooctane ring system is assembled by a three-step process featuring a thermally induced cycloaddition followed by a 1,3-benzothiolium ion mediated cyclization onto an enol or silyl enol ether double bond.
