Diverse alkanones by catalytic carbon insertion into the formyl C-H bond. Concise access to the natural precursor of achyrofuran.
Over a century ago, the first reactions of diazomethane with aldehydes delivered methyl ketones. In the interim, aldehydes have been homologated with trimethylsilyldiazomethane, diazoacetates, and aryldiazomethanes, on rare occasion with catalysis. This work describes a mild procedure for convergent ketone assembly from nonstabilized diazoalkanes, including examples of chiral ketone synthesis with disubstituted (internal) nucleophiles. The method's remarkable tolerance to steric crowding is showcased in a simple approach to achyrofuran, a complex dibenzofuran.
Wommack
Andrew J
AJ
Department of Chemistry, Eugene F. Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Moebius
David C
DC
Travis
Austin L
AL
Kingsbury
Jason S
JS
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003924:Diabetes Mellitus, Type 2 / Q000188:drug therapy; D015195:Drug Design; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry; D007004:Hypoglycemic Agents / Q000138:chemical synthesis* / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*
D005663:Furans; D007004:Hypoglycemic Agents; D007659:Ketones; C452205:achyrofuran; D002244:Carbon