Catalytic, asymmetric transannular aldolizations: total synthesis of (+)-hirsutene.
We report an asymmetric, catalytic transannular aldolization that provides polycyclic products useful for natural product synthesis. We found that a proline-derivative catalyzes the transannular aldol reaction of 1,4-cyclooctanediones to the corresponding cyclic beta-hydroxy ketones in good yields and with high enantioselectivities. The utility of our reaction has been demonstrated in a total synthesis of (+)-hirustene.
Chandler
Carley L
CL
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany.
List
Benjamin
B
D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D000081223:Polycyclic Sesquiterpenes; D011392:Proline / Q000031:analogs & derivatives; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000447:Aldehydes; D007659:Ketones; D011083:Polycyclic Compounds; D000081223:Polycyclic Sesquiterpenes; D012717:Sesquiterpenes; C486985:hirsutene; D011392:Proline