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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.

Abstract : 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.
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01116313
Contributor : Laurent Jonchère <>
Submitted on : Friday, February 13, 2015 - 9:41:41 AM
Last modification on : Thursday, March 5, 2020 - 2:06:22 PM

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van Ha Vu, Fadila Louafi, Nicolas Girard, Ronan Marion, Thierry Roisnel, et al.. 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.. Journal of Organic Chemistry, American Chemical Society, 2014, 79 (8), pp.3358-73. ⟨10.1021/jo500104c⟩. ⟨hal-01116313⟩

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