Enantioselective route to 5-methyl- and 5,7-dimethyl-6,7-dihydro-5H-dibenz[c,e]azepine: secondary amines with switchable axial chirality.
(-)-5-Methyl-6,7-dihydro-5H-dibenz[c,e]azepine 4, a new secondary amine featuring an axis-center stereochemical relay, was prepared enantioselectively from 2'-acetylbiphenyl-2-carboxylic acid, using (R)-2-phenylglycinol as an auxiliary for the control of both elements of chirality. The biaryl axis in 4 preferentially adopts the aS-configuration, with the methyl substituent pseudoequatorial, but conversion into the corresponding N-Boc derivative locks the axis into the aR-configuration, as predicted on the basis of molecular mechanics calculations.
Pira
Silvain L
SL
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK.
Wallace
Timothy W
TW
Graham
Jonathan P
JP
D000588:Amines / Q000737:chemistry; D002384:Catalysis; D003984:Dibenzazepines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D000588:Amines; D003984:Dibenzazepines