氯甲基磺酰乙烯和二氯甲基磺酰乙烯：用于串联狄尔斯-阿尔德/拉姆伯格-巴克伦德反应的新型试剂。

Chloromethanesulfonylethene and dichloromethanesulfonylethene: new reagents for tandem Diels-Alder/Ramberg-Bäcklund reactions.

作者信息

Block Eric, Jeon Hak Rim, Zhang Shao-Zhong, Dikarev Evgeny V

机构信息

Department of Chemistry, State University of New York at Albany, Albany, New York 12222, USA.

出版信息

Org Lett. 2004 Feb 5;6(3):437-40. doi: 10.1021/ol0363523.

DOI:10.1021/ol0363523

PMID:14748612

Abstract

[reaction: see text] Chloromethanesulfonylethene (3a) and dichloromethanesulfonylethene (3b) were prepared by oxidation of the adducts of ethylene and ClCH(2)SCl or Cl(2)CHSCl, respectively, followed by NaHCO(3) dehydrochlorination. With dienes, 3a gave Diels-Alder adducts that, with base, underwent Ramberg-Bäcklund reaction, giving products corresponding to the adducts of the dienes and allene. Similarly, 3b gave Diels-Alder adducts that, with base in the presence of the novel chlorine source MeSO(2)CCl(3), cleanly afforded products corresponding to the adducts of the dienes and 1,1-dichloropropa-1,2-diene.

摘要

[反应：见正文] 分别通过氧化乙烯与ClCH(2)SCl或Cl(2)CHSCl的加合物，然后进行NaHCO(3)脱氯化氢反应，制备了氯甲基磺酰乙烯（3a）和二氯甲基磺酰乙烯（3b）。对于二烯烃，3a生成狄尔斯-阿尔德加合物，该加合物在碱的作用下发生拉姆贝格-巴克伦德反应，得到与二烯烃和丙二烯的加合物相对应的产物。类似地，3b生成狄尔斯-阿尔德加合物，该加合物在新型氯源MeSO(2)CCl(3)存在下与碱反应，顺利得到与二烯烃和1,1-二氯丙-1,2-二烯的加合物相对应的产物。