133535-68-9Relevant academic research and scientific papers
Carbocyclic Amino Ketones by Bredt's Rule-Arrested Kulinkovich-de Meijere Reaction
Finn, Paul B.,Derstine, Brenden P.,Sieburth, Scott McN.
supporting information, p. 2536 - 2539 (2016/02/18)
The TiII-mediated formation of cyclopropylamines from alkenes and amides, the Kulinkovich-de Meijere reaction, involves two carbon-carbon bond-forming steps. Strategic use of a tricyclic intermediate can arrest the process if the second step requires formation of a bridgehead double bond. Use of this Bredt's rule constraint results in the production of carbocyclic amino ketones, key alkaloid building blocks. Frustrated by Bredt's rule: An inability to consummate a Kulinkovich-de Meijere cyclopropanation that would involve a bridgehead double bond transforms the reaction into a transannular cyclization of an unsaturated lactam yielding an amino ketone product with potential for alkaloid synthesis.
Substitution reactions of 2-phenylsulphonyl-piperidines and -pyrrolidines with carbon nucleophiles: Synthesis of the pyrrolidine alkaloids norruspoline and ruspolinone
Brown, Dearg S.,Charreau, Philippe,Hansson, Thomas,Ley, Steven V.
, p. 1311 - 1328 (2007/10/02)
Several 2-phenylsulphonyl-piperidines and -pyrrolidines were prepared from the corresponding N-acyl aminals by treatment with benzenesulphinic acid. On reaction with various carbon nucleophiles these sulphones gave good yields of substitution products. Typical nucleophiles used in these studies were organometallic reagents derived from Grignard reagents and zinc halide together with silyl enol ethers, silyl ketene acetals, allylsilanes and trimethylsilyl cyanide in the presence of a Lewis acid. These methods were employed in the synthesis of two natural product alkaloids; Norruspoline (38) and Ruspolinone (40).
