Intramolecular allenolate acylations in studies toward a synthesis of FR182877.
During our efforts to synthesize the cytotoxic natural product FR182877, we discovered intramolecular reductive acylations that offer a stereocontrolled alternative to the classical Knoevenagel condensation for the formation of alpha-alkylidene beta-keto-delta-lactones. Other progress toward a synthesis of FR182877 includes a pi-allyl Stille coupling and a bromo Horner-Wadsworth-Emmons reaction that forms a 12-membered ring. Structural relationships among FR182877, hexacyclinic acid, macquarimicin A, and cochleamycin A are also discussed. [reaction: see text]
Vanderwal
C D
CD
The Skaggs Institute for Chemical Biology and Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, USA.
Vosburg
D A
DA
Sorensen
E J
EJ
D000215:Acylation; D000970:Antineoplastic Agents / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009281:Naphthalenes / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000970:Antineoplastic Agents; C408303:FR 182877; D009281:Naphthalenes; D011083:Polycyclic Compounds; C110055:allenolic acid