Total synthesis of kendomycin featuring intramolecular Dötz benzannulation.
One-step formation of the ansa-skeleton realized the synthesis of kendomycin, an ansa-type quinone methide. The Fischer carbene complex derived from the ansa-chain portion was subjected to the intramolecular Dotz benzannulation to afford the desired oxametacyclophane with exclusive regioselectivity. Subsequent Claisen rearrangement, ortho oxidation of the resulting phenol derivative, and mild transformation from p-quinone to p-quinone methide on a silica gel plate furnished kendomycin.
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Kyosuke
K
Tanaka
Masahito
M
Watanabe
Kodai
K
Ishibashi
Hiroshi
H
Matsuyama
Yoko
Y
Saikawa
Masaya
M
Nakata
D002857:Chromium / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D017828:Rifabutin / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
C485395:kendomycin; D002857:Chromium; D017828:Rifabutin; C030011:carbene; D008697:Methane