Studies of electron-depleted thiocarbonyl compounds—IV

Hetero-Diels-Alder reactions of chlorodithioformates with acyclic 1,3-dienes

“…Our earlier review of chlorodithioformates could not report any examples of their dienophilic as opposed to their well-documented 1,3-dipolarophilic properties [1] and a somewhat earlier report from our laboratory explicitly stated that such compounds do not react with buta-1,3-diene [2]. An attempted hetero-Diels-Alder reaction between trichloromethyl chlorodithioformate Cl-CSSCCl 3 and anthracene only led to Friedel-Crafts substitution with no observable intermediate cycloadduct [3].…”

Sulfur, An Important Element in my Life

“…C-Sulfonyldithioformates 54 react with carbanions in a number of ways, initiated by carbophilic and/or thiophilic attack of the carbanion on the thiocarbonyl group of 54 [134,135].…”

“…The thiocarbonyl group of C-sulfonyldithioformates 54 readily participates in heteroDiels-Alder reactions with simple alka-1,3-dienes and with cyclopenta-1,3-diene [134,136]. C-Sulfonyldithioformates 54 react with anthracene and 9-methylanthracene in a hetero-Diels-Alder fashion.…”

“…Thermal ene reactions between C-sulfonyldithioformates 54 and tetramethylallene (2,4-dimethylpenta-2,3-diene) are especially facile [134]. In addition to these thermal ones photochemical ene reactions of 54 have also been observed.…”

A convenient access to ring unsaturated cyclopentanecarbodithioates via hetero-Diels–Alder chemistry

“…2 An attempted hetero-Diels-Alder reaction between trichloromethyl chlorodithioformate, Cl-CSSCCl 3 , and anthracene led only to Friedel-Crafts substitution with no observable intermediate cycloadduct. On the other hand, several closely related thiocarbonyl compounds such as thiophosgene, 4 cyanodithioformates NC-CSSR, 5 C-sulfonyldithioformates R 1 SO 2 -CSSR, 2,6 and phosphonyldithio-formates, (R 1 O) 2 PO-CSSR , 2,7 do exhibit a rich hetero-Diels-Alder chemistry with 1,3-dienes.…”