119980-65-3Relevant articles and documents
STEREOSPECIFICITY IN THE PICTET-SPENGLER REACTION. ENANTIOSPECIFIC SYNTHESIS OF (6S,10S)-(-)-5-METHYL-9-OXO-12-BENZYL-6,7,8,9,10,11-HEXAHYDRO-6,10-IMINO-5H-CYCLOOCTINDOLE, A TEMPLATE FOR PREPARATION OF MACROLINE/SARPAGINE ALKALOIDS
Zhang, Lin-Hua,Bi, Ying-Zhi,Yu, Fu-Xiang,Menzia, Gerald,Cook, James M.
, p. 517 - 547 (2007/10/02)
The synthesis of the tetracyclic ketone was carried out in enantiospecific fashion (>98percent ee) via the 1,3-transfer of chirality from Na-methyl, Nb-benzyl tryptophan methyl ester to the trans diastereomer in the Pictet-Spengler reaction.Although the condensation of 14 with aldehyde (15) in refluxing benzene generated the tetrahydro β-carbolines (4b/5b) in a kinetic ratio (72:28), epimerization (C-1) of the cis diastereomer into the trans isomer occurred stereospecifically under acidic conditions.Dieckmann cyclizatin of either the Na-methyl, Nb-benzyl-cis-(+)-5b or trans-(-)-4b diastereomer provided the cis-bicyclo-azanonane system at approximately the same rate, although the β-keto esters were antipodal, in contrast to results reported in the Na-benzyl series by Magnus.