Zhao Changjia, Yan Jun, Xi Zhenfeng
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
J Org Chem. 2003 May 30;68(11):4355-60. doi: 10.1021/jo034107r.
Three different components involving alkynes, ethylene, and aldehydes were selectively integrated in a one-pot procedure to afford homoallyl ketones in good yields, via an effective combination of zirconocene-mediated C-C bond forming reactions and Lewis acid mediated organic transformation. Mechanistic studies revealed that a formal Oppenauer oxidation of seven-membered oxazirconacycles, generated in situ from the reactions of zirconacyclopentenes and aldehydes, was promoted by Lewis acid-aldehyde adducts. As a whole, the first aldehyde was incorporated into the product and the second aldehyde was reduced to an alcohol. Multiply deuterated homoallyl ketones could be readily prepared in high yields with more than 98% deuterium incorporation by using this method.
通过锆茂介导的碳-碳键形成反应与路易斯酸介导的有机转化的有效结合，在一锅法中选择性地整合了涉及炔烃、乙烯和醛的三种不同组分，以良好的产率得到高烯丙基酮。机理研究表明，由锆环戊烯与醛的反应原位生成的七元氧氮锆环的形式上的欧芬脑尔氧化反应由路易斯酸-醛加合物促进。总体而言，第一个醛被并入产物中，第二个醛被还原为醇。通过使用该方法，可以容易地以高产率制备氘掺入率超过98%的多重氘代高烯丙基酮。
