Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ. Paris-Sud, 91405 Orsay, France.
Chemistry. 2013 Jul 8;19(28):9358-65. doi: 10.1002/chem.201300836. Epub 2013 Jun 5.
A general methodology for the stereoselective synthesis of 2-(2-hydroxyalkyl)piperidine alkaloids by ring-rearrangement metathesis of nitroso Diels-Alder cycloadducts is reported. The approach is illustrated by the formal synthesis of porantheridine and the total synthesis of andrachcinidine through a diastereodivergent allylation of an N-alkoxy bicyclic lactam. The asymmetric synthesis of the latter alkaloid provides new insights into the configurational stability of cycloadducts between chloronitroso reagents and cyclopentadiene.
报道了一种通过硝基亚胺 Diels-Alder 环加成物的环重排复分解反应来立体选择性合成 2-(2-羟烷基)哌啶生物碱的一般方法。该方法通过 N-烷氧基双环内酰胺的立体定向性烯丙基化反应，以正式合成波那替林啶和阿德拉嗪啶的全合成为例进行了说明。后者生物碱的不对称合成为氯代亚硝酰试剂与环戊二烯之间的环加成物的构型稳定性提供了新的见解。
