%0 Journal Article %A Pearson, William H. %A Mans, Douglas M. %A Kampf, Jeff W. %D 2004 %T Cycloadditions of 2-Azaallyllithium Species with Conjugated Polyenes %U https://acs.figshare.com/articles/journal_contribution/Cycloadditions_of_2_Azaallyllithium_Species_with_Conjugated_Polyenes/3349156 %R 10.1021/jo030306z.s001 %2 https://acs.figshare.com/ndownloader/files/5188468 %K R 2 %K azaallyllithium %K novel bridged azabicyclic compounds %K cyclic dienes %K species %K azabicyclo %K R 1 %K CH %K diastereoselective endo fashion %K Azaallyllithium %X 2-Azaallyllithium species [R1CH(−)NC(X)R2Li(+), where R1 and R2 are alkyl and X = OMe] were generated by tin−lithium exchange of (2-azaallyl)stannanes and underwent [π4s+π2s] and [π6s+π4s] cycloadditions with cyclic dienes and trienes, respectively, to generate novel bridged azabicyclic compounds in a highly diastereoselective endo fashion. The periselectivity using cycloheptatriene was modest, producing a 1:1 mixture of [π6s+π4s] and [π4s+π2s] adducts. The reactions of 2-azaallyllithium species with dienes proceeded by a [π4s+π2s] pathway. The cycloadducts derived from cyclic 2-azaallyllithium species possess the 7-azabicyclo[2.2.1]heptane (tropane) or 8-azabicyclo[3.2.1]octane ring system and have been elaborated into cocaine-like analogues. %I ACS Publications