Synthesis of (+/-)-hamigeran B, (-)-hamigeran B, and (+/-)-1-epi-hamigeran B: use of bulky silyl groups to protect a benzylic carbon-oxygen bond from hydrogenolysis.
Enone 42 was converted into diene 56, which was then subjected to hydrogenation. Use of the tert-butyldimethylsiloxy groups enforces facial selectivity and protects the C(5) oxygen from hydrogenolysis. The resulting product (55) is easily converted into hamigeran B (1), a marine natural product with powerful activity against herpes and polio viruses. Optically pure enone 73 was made by use of a Meyers' auxiliary and converted into (-)-hamigeran B with the natural absolute configuration.
Clive
Derrick L J
DL
Chemistry Department, University of Alberta, Edmonton, Alberta, Canada. derrick.clive@ualberta.ca
Wang
Jian
J
D000818:Animals; D001593:Benzyl Compounds / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D003500:Cyclization; D006865:Hydrogenation; D015394:Molecular Structure; D009285:Naphthoquinones / Q000138:chemical synthesis*; D010100:Oxygen / Q000737:chemistry; D011161:Porifera / Q000737:chemistry; D012825:Silicon / Q000737:chemistry; D013237:Stereoisomerism
D001593:Benzyl Compounds; D009285:Naphthoquinones; C483756:hamigeran B; D002244:Carbon; D010100:Oxygen; D012825:Silicon