膦烯酮和beta-膦内酰胺合成研究

beta-膦内酰胺是beta-内酰胺的含磷类似物，目前尚无有效的合成方法。基于我们课题组近十年来关于通过烯酮与亚胺合成beta-内酰胺和烯砜与亚胺合成beta-磺内酰胺，及其反应机理和立体化学方面的研究基础。在本项目中拟开展通过膦烯酮与亚胺反应来合成beta-膦内酰胺类化合物研究。通过氧代磷杂环戊烯与二氯卡宾的加成及重排得到氧代磷杂环己二烯，其与丁炔二甲酸酯的Diels-Alder环加成产物发生逆Diels-Alder环加成就可以生成烃基膦烯酮。用五硫化二磷对Diels-Alder环加成产物进行处理，再发生逆Diels-Alder环加成就可以生成烃基硫代膦烯酮。研究膦烯酮的亲电活性顺序。通过烃基膦烯酮和亚胺来实现beta-膦内酰胺的合成，还将研究膦烯酮与两分子小位阻亚胺生成六元环产物。以及烃基膦烯酮与亚胺形成beta-膦内酰胺和六元环产物的立体化学及其反应机理。

Beta-phospholactams are phosphorus analogs of beta-lactams. To date, no efficient synthetic methods have been developed for their preparation. On the basis of our investigations into the synthesis, mechanism, and stereochemistry in the preparations of beta-lactams and beta-sultams from ketenes and sulfenes with imines during recent ten years, we plan to study the synthesis of beta-phospholactams from alkylidenephosphinates and imines in the current project. Dihydrophosphinine oxides are first prepared from 3-phospholene oxides and dichlorocarbene followed by a rearrangement and undergo Diels-Alder reaction with dimethyl butynedioate to give rise to bicyclic adducts, which further undergo a retro-Diels-Alder reaction, affording alkylidenephosphinates. We will study electrophilic order of different alkylidenephosphinates and realize the preparation of beta-phospholactams from alkylidenephosphinates and imines. We will also investigate the synthesis of six-membered ring products, 1,5,2-diazaphosphinane 2-oxides, from alkylidenephosphinates and less steric imines. The mechanisms and stereochemistry on both of reactions will be investigated as well in the project.