Department of Chemistry, Analytical and Biological Chemistry Research Facility, University College Cork, Ireland.
Org Biomol Chem. 2011 Apr 7;9(7):2452-72. doi: 10.1039/c0ob00805b. Epub 2011 Feb 21.
Synthetically versatile conjugate addition of a range of carbon, nitrogen, oxygen, sulfur and selenium nucleophiles to the highly functionalised 2-thio-3-chloroacrylamides is described. The stereochemical and synthetic features of this transformation are discussed in detail. In most instances, the nucleophile replaces the chloro substituent with retention of stereochemistry. With the oxygen nucleophiles, a second addition can occur leading to acetals, while with the nitrogen nucleophiles, E-Z isomerism occurs in the resulting enamine derivatives. The ratio of the E/Z isomers can be rationalised on the basis of the substituent and the level of oxidation.
描述了一系列碳、氮、氧、硫和硒亲核试剂对高度功能化的 2-硫代-3-氯丙烯酰胺的综合多功能共轭加成。详细讨论了这种转化的立体化学和合成特征。在大多数情况下，亲核试剂取代氯取代基，同时保留立体化学。对于氧亲核试剂，可以发生第二次加成，导致缩醛的形成，而对于氮亲核试剂，在得到的烯胺衍生物中会发生 E-Z 异构化。根据取代基和氧化水平，可以合理推断 E/Z 异构体的比例。
