Some Unusual Reactions of 3,5-Di-tert-butyl-1,2-dithiolium Perchlorate with Nucleophiles
作者:Klaus Hartke、Andreas Kraska
DOI:10.1055/s-1997-1158
日期:1997.2
3,5-Di-tert-butyl-1,2-dithiolium perchlorate (4) reacts with ethanol, piperidine or metal cyclopentadienides by carbophilic attack to form the addition products 2, 3 and 5 at the sterically hindered 3-position. Methyl- and phenyllithium cleave the 1,2-dithiolium ring in 4 by thiophilic attack giving rise to the β-methylthio- or (β-phenylthio)prop-2-enones 7 a, b. Nitromethane condenses with 4 in a complex reaction sequence to furnish the β-cyanoprop-2-enone 12.
3,5-二叔丁基-1,2-二硫鎓高氯酸盐(4)与乙醇、哌啶或金属环戊二烯化物通过亲碳攻击反应,在位阻3位形成加成产物2、3和5。甲基-和苯基锂通过亲硫攻击将1,2-二硫环裂解为4,产生β-甲硫基-或(β-苯硫基)丙-2-烯酮7 a,b。硝基甲烷与 4 在复杂的反应序列中缩合,得到 β-cyanoprop-2-enone 12。