Asymmetric total synthesis of (-)-awajanomycin.
The first asymmetric total synthesis of the unnatural enantiomer of cytotoxic awajanomycin (1) is reported. The synthetic approach features first a convergent strategy using the cross-olefin metathesis reaction to link the lipid side chain 2 and the piperidinone core structure 3. The second feature of the synthesis resides on the construction of segment 3 from the building block 5 via a three-component tandem reaction on the mixed imide 12. Through this work, the stereochemistry at C-11 and the absolute configuration of awajanomycin were established as 3R,5R,6S,8S,11S.
Department of Chemistry and Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, PR China.
Rui
R
Fu
Jie
J
Chen
Lu-Chuan
LC
Guo
Jian-Liang
JL
Ye
Yuan-Ping
YP
Ruan
Pei-Qiang
PQ
Huang
D018360:Crystallography, X-Ray; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
D007769:Lactams; C514409:awajanomycin