(+)-Zwittermicin A. Rapid assembly of C9-C15 and a formal total synthesis.
A short, enantioselective synthesis of the C9-C15 portion of (+)-zwittermicin A is reported that exploits directional functionalization of the known hepta-2,5-diyne-1,7-diol by partial reduction of the two triple bonds followed by Sharpless asymmetric epoxidation and boron-directed double ring-opening with sodium azide under Miyashita conditions. Subsequent desymmetrization of the C(2)-symmetric diazidotetraol product converges upon (-)-3--the enantiomer of the key intermediate of our earlier structural proof and synthesis of (-)-zwittermicin A--and constitutes a formal synthesis of (+)-zwitttermicin A.
Rogers
Evan W
EW
Department of Chemistry and Biochemistry and Skaggs School of Pharmacy, University of California, San Diego, 9500 Gilman Dr., La Jolla, California 92093, USA.
Molinski
Tadeusz F
TF
D015394:Molecular Structure; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D010455:Peptides; C088290:zwittermicin A