Protected cyanohydrins in the synthesis of rotenoids: (+/-)-munduserone and (+/-)-cis-12a-hydroxymunduserone.
Short synthetic routes to the natural products (+/-)-munduserone 1 and (+/-)-cis-12a-hydroxymunduserone 9 from protected cyanohydrin 5 and nitrochromene 4 are described. The key coupling reaction of 4 and 5 gave under inverse addition conditions 9 (28%) and 2b (21%), while under normal addition conditions, a mixture of 9 (20%), dehydromunduserone 10 (9%), and enone 2b (10%) was obtained. (+/-)-Munduserone 1 is easily obtained from both 2b and 9 by 10% methanolic HCl (86%) and Zn/AcOH (71%) treatments, respectively.
Granados-Covarrubias
Evin H
EH
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, México, 04510, D.F., México.
Maldonado
Luis A
LA
D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D012402:Rotenone / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
D009570:Nitriles; C543755:cis-12a-hydroxymunduserone; C430593:cyanohydrin; C543754:munduserone; D012402:Rotenone