N-methoxy-N-acylnitrenium ions: application to the formal synthesis of (+/-)-desmethylamino FR901483.
[reaction: see text] The formal synthesis of (+/-)-desmethylamino FR901483 (2) is described. Construction of the unique azatricyclic skeleton of 2 was accomplished by a sequence which involved (i) preparation of dienone 7 by an N-methoxy-N-acylnitrenium ion-induced spirocyclization, (ii) formation of 2-azabicyclo[3.3.1]nonane 5 by the 6-(pi-exo)-exo-trig radical cyclization of 1,7-enyne 6, and (iii) installation of the C-5 p-methoxybenzyl side chain by Lewis acid-mediated alkylation of silyl enol ether 18.
Wardrop
D J
DJ
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607-7061, USA. wardropd@uic.edu
Zhang
W
W
D001372:Aza Compounds / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000737:chemistry*; D007166:Immunosuppressive Agents / Q000138:chemical synthesis*; D009943:Organophosphorus Compounds / Q000138:chemical synthesis*; D013141:Spiro Compounds / Q000737:chemistry*
D001372:Aza Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D001952:Bridged-Ring Compounds; C098358:FR 901483; D007166:Immunosuppressive Agents; D009943:Organophosphorus Compounds; D013141:Spiro Compounds