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.
Tanaka
Kyosuke
K
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Watanabe
Masahito
M
Ishibashi
Kodai
K
Matsuyama
Hiroshi
H
Saikawa
Yoko
Y
Nakata
Masaya
M
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