Total synthesis and structure revision of stachybotrys spirolactams.
The spirolactam structure 1 reported in 1996 by Roggo et al. has been enantioselectively synthesized in 20 steps from (+)-Wieland-Miescher ketone. Spectra of this synthetic lactam differed from those of the natural spirolactam from the Roggo group, leading to the hypothesis that the natural lactam may be the regioisomer 27, a structure previously ascribed by Jarvis et al. to the natural product stachybotrylactam. This hypothesis was confirmed by the first total synthesis of (-)-stachybotrylactam (27). Double reductive amination of two molecules of aldehyde 29 with one molecule of l-lysine led by analogous chemistry to the first synthesis of the pseudosymmetric "dimer" 30, whose spectra corresponded to those of the natural "dimer" originally assigned structure 5 by the Roggo group.
Deng
Wei-Ping
WP
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Zhong
Min
M
Guo
Xiao-Chuan
XC
Kende
Andrew S
AS
D000447:Aldehydes / Q000737:chemistry; D000586:Amination; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D008239:Lysine / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis; D013191:Stachybotrys / Q000737:chemistry*; D013237:Stereoisomerism
D000447:Aldehydes; D007769:Lactams; D013141:Spiro Compounds; D008239:Lysine