Diastereoselective phenol para-alkylation: access to a cross-conjugated cyclohexadienone en route to resiniferatoxin.
We document a route for the synthesis of a densely functionalized spiro-fused 2,5-cyclohexadienone as an intermediate for the synthesis of resineferatoxin. The strategy is based on an unprecedented diastereoselective, intramolecular phenol para-alkylation to a cross-conjugated cyclohexadienone. In the course of these synthetic studies we developed rapid access to a chiral nitrile possessing a quaternary stereocenter and disclose an unusual acetal rearrangement from a dioxane, which favors the corresponding dioxepane.
Ritter
Tobias
T
Laboratorium für Organische Chemie, ETH-Hönggerberg, HCI, H335, CH-8093 Zürich, Switzerland.
Zarotti
Pablo
P
Carreira
Erick M
EM
D000478:Alkylation; D003510:Cyclohexanes / Q000737:chemistry*; D053138:Cyclohexenes; D004224:Diterpenes / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D019800:Phenol / Q000737:chemistry*; D013237:Stereoisomerism
D003510:Cyclohexanes; D053138:Cyclohexenes; D004224:Diterpenes; C507608:cyclohexadienone; D019800:Phenol; C024353:resiniferatoxin