Stereoselective and Stereospecific Triflate‐Mediated Intramolecular Schmidt Reaction: Ready Access to Alkaloid Skeletons**

The stereoselectivity and stereospecificity of the triflate-mediated intramolecular Schmidt reaction substituted 3-(1-azidocyclohexyl)propanol derivatives leading to octahydro-1H-pyrrolo[1,2-a]azepine, structural skeleton several important families alkaloids such as Stemona alkaloids, has been examined. involves an initial SN2 between azide moiety triflate affording intermediate spirocyclic aminodiazonoium salt that undergoes expected 1,2-shift/N2-elimination followed by hydride-mediated iminium reduction. Remarkably, chiral alcohols are converted azabicyclic derivative with no or limited racemization. asymmetric alcohol center controls diastereoselectivity whole process, formation one out four possible diastereoisomers disubstituted octahydro-1H-pyrrolo[1,2-a]azepine. origin is rationalized based on theoretical calculations. concise synthesis (−)-(cis)-3-propylindolizidine (−)-(cis)-3-butyllehmizidine, two found in venom workers ant Myrmicaria melanogaster, reported.