%0 Journal Article %T Electrochemical access to 8-(1-phenyl-ethyl)-1,4-dioxa-8-aza-spiro[4.5]decane-7-carbonitrile. Application to the asymmetric syntheses of (+)-myrtine and alkaloid (+)-241D. %+ Institut des Sciences Chimiques de Rennes (ISCR) %+ Département de Chimie %A Vu, van Ha %A Louafi, Fadila %A Girard, Nicolas %A Marion, Ronan %A Roisnel, Thierry %A Dorcet, Vincent %A Hurvois, Jean-Pierre %< avec comité de lecture %@ 0022-3263 %J Journal of Organic Chemistry %I American Chemical Society %V 79 %N 8 %P 3358-73 %8 2014-04-18 %D 2014 %R 10.1021/jo500104c %M 24670203 %Z Chemical SciencesJournal articles %X The total syntheses of both enantiomers of trans-quinolizidine (+)-myrtine and cis-2,4,6-trisubstituted piperidine alkaloid (+)-241D are reported here. Our approach was based on the N-Boc-directed metalation of enantiopure 4-piperidone (-)-11, which was prepared in four steps from α-amino nitrile 6 through a stereoselective alkylation-reduction decyanation process. α-Amino nitrile 6 was prepared at the anode through electrochemical oxidation of 4-piperidone (+)-5. In our study, α-phenylethylamine (α-PEA) allowed an efficient 1-3 stereoinduction, and an orthogonal cleavage of the N-Boc protecting group in piperidone derivatives was carried out by stirring them in a suspension of SnCl4·(Et2O)2 complex in diethyl ether. When appropriate, the er's were determined by proton and carbon NMR spectroscopy utilizing (+)-tert-butylphenylphosphinothioic acid and (+)-DBTA as chiral solvating agents. %G English %L hal-01116313 %U https://univ-rennes.hal.science/hal-01116313 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR-CD %~ SCR-PNSCM %~ STATS-UR1 %~ UR1-SPM %~ ISCR-PRATS %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ ISCR-CORINT %~ UR1-SDLM %~ UR1-SDLMJONCH %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ ISCR-CORINT1 %~ UR1-MMS %~ ISCR-CORINT3 %~ TEST2-HALCNRS %~ TEST3-HALCNRS