396100-81-5Relevant articles and documents
Chiral lithium amide base-mediated rearrangement of meso-cyclohexene oxides: Asymmetric synthesis of amino- and aziridinocyclohexenols
O'Brien, Peter,Pilgram, Christopher D.
, p. 523 - 534 (2007/10/03)
Two different chiral lithium amide base routes for the synthesis of amino- and aziridino-containing cyclohexenols have been explored. The first strategy involved the diastereoselective preparation of novel meso-aziridinocyclohexene oxides and their subsequent enantioselective rearrangement using chiral bases. In this approach, the diphenyl-phosphinoyl nitrogen protecting group proved optimal and aziridinocyclohexenols of 47-68% ee were obtained. Of particular note was the smooth rearrangement of the epoxide to an allylic alcohol in the presence of an aziridine: under optimised chiral base conditions, the aziridine remained essentially unaffected. A second more straightforward strategy for introduction of an amino functionality was also investigated: (1S,4R,5S)- and (1R,4R,5S)-4,5-bis(tert-butyldimethylsilyloxy)cyclohex-2- enols, readily prepared in >95% ee using a chiral base approach, were subjected to Mitsunobu substitution using a sulfonamide and Overman rearrangement.
Chiral base route to cyclic polyols: Asymmetric synthesis of aminodeoxyconduritols and conduritol F
De Sousa, Simon E.,O'Brien, Peter,Pilgram, Christopher D.
, p. 8081 - 8083 (2007/10/03)
A chiral base route from a meso cyclohexene oxide to an allylic alcohol provides key intermediates for the synthesis of cyclic polyols. A Mitsunobu approach and an Overman rearrangement approach transform allylic alcohols into some aminodeoxyconduritols (95% ee). Elaboration of a chiral enone (89% ee) via (i) α-hydroxylation and (ii) stereoselective reduction completes a high yielding synthesis of the tetraacetate of conduritol F.
