Thermal elimination of diethyldithiocarbamates and application in the synthesis of (+/-)-ferrugine.
Dithiocarbamate-substituted lactams, prepared through group-transfer cyclization reactions of carbamoyl radicals, undergo a Chugaev-like thermal elimination of the dithiocarbamate group in refluxing diphenyl ether to form alpha,beta- and/or beta,gamma-unsaturated amides, depending on the structure of the starting material. This reaction sequence was used to prepare an unsaturated [3.2.2] bridged bicyclic amide, which was converted in a one-pot procedure to the 8-azabicyclo[3.2.1]octane ring system of the tropane alkaloid ferrugine by treatment with phenyllithium followed by aqueous sodium hydroxide.
Ahmed
Shamim
S
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK.
Baker
Luke A
LA
Grainger
Richard S
RS
Innocenti
Paolo
P
Quevedo
Camilo E
CE
D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D003500:Cyclization; D004050:Ditiocarb / Q000737:chemistry*; D007769:Lactams / Q000737:chemistry; D013237:Stereoisomerism; D013696:Temperature
D019086:Bridged Bicyclo Compounds, Heterocyclic; D007769:Lactams; C418212:ferruginine; D004050:Ditiocarb