Stereospecific rearrangements during the synthesis of pyrrolidines and related heterocycles from cyclizations of amino alcohols with vinyl Sulfones.
Conjugate additions of amino alcohols derived from alpha-amino acids to vinyl sulfones, followed by N-benzylation, chlorination, and intramolecular alkylation, provide a convenient route to substituted pyrrolidines. The process is accompanied by the stereospecific rearrangement of substituents from the alpha-position of the amine to the beta-position of the product and takes place via the corresponding aziridinium ion intermediates. Another type of rearrangement was observed during the reaction of (2-piperidine)methanol or 2-(2-piperidine)ethanol with phenyl trans-1-propenyl sulfone, in which the methyl group appears to migrate from the beta- to the alpha-position of the sulfone moiety. This process involves the isomerization of phenyl trans-1-propenyl sulfone to phenyl 2-propenyl sulfone by the addition-elimination of catalytic benzenesulfinate anion to the former vinyl sulfone, followed by conjugate addition of the amino group to the latter sulfone. Chlorination and intramolecular alkylation then afford the corresponding rearranged indolizidine and quinolizidine derivatives, respectively.
Back
Thomas G
TG
Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4. tgback@ucalgary.ca
Parvez
Masood
M
Zhai
Huimin
H
D000478:Alkylation; D000605:Amino Alcohols / Q000737:chemistry*; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D011759:Pyrrolidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
D000605:Amino Alcohols; D006571:Heterocyclic Compounds; D011759:Pyrrolidines; D013450:Sulfones; D014753:Vinyl Compounds