Back Thomas G, Parvez Masood, Zhai Huimin
Department of Chemistry, University of Calgary, Calgary, AB, Canada T2N 1N4.
J Org Chem. 2003 Nov 28;68(24):9389-93. doi: 10.1021/jo0350864.
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.
源自α-氨基酸的氨基醇与乙烯基砜进行共轭加成，随后进行N-苄基化、氯化和分子内烷基化反应，为合成取代吡咯烷提供了一条便捷途径。该过程伴随着取代基从胺的α位立体定向重排至产物的β位，且通过相应的氮杂环丙烷离子中间体进行。在(2-哌啶基)甲醇或2-(2-哌啶基)乙醇与苯基反式-1-丙烯基砜的反应中观察到了另一种重排类型，其中甲基似乎从砜部分的β位迁移至α位。该过程涉及通过催化苯亚磺酸盐阴离子对前一种乙烯基砜进行加成-消除反应，使苯基反式-1-丙烯基砜异构化为苯基2-丙烯基砜，随后氨基对后一种砜进行共轭加成。氯化和分子内烷基化反应分别得到相应的重排中氮茚和喹嗪衍生物。
