Selected Reactions on (R)Ph 2 PNS 3 N 3 Heterocycles: Exploration of chemical behavior and reactivity

Reactions of (R)Ph 2 PNS 3 N 3 heterocycles with olefins such as norbornadiene, norbornene and dicyclopentadiene have yielded different results. Like Ph 3 PNS 3 N 3 , (R)Ph 2 PNS 3 N 3 (R = C 4 H 8 N, C 5 H 10 N, C 6 H 12 N, CH 3 NC 4 H 8 N and OC 4 H 8 N) compounds have given the cycloaddition products (R)Ph 2 PNS 3 N 3 · C 7 H 8 (yield 41 ‐ 62%) with norbornadiene, while norbornene and dicyclopentadiene have not produced the corresponding adducts under identical conditions. With Ph 3 PNS 3 N 3 both norbornene and dicyclopentadiene have given the ring expanded heterocycle, 1,5‐[Ph 3 PN] 2 S 4 N 4 in ca. 65% yield. The solution phase decomposition studies of (secondary amino) Ph 2 PNS 3 N 3 derivatives have lead to the formation of (R)Ph 2 PNH 2 + X − , while (primary amino) Ph 2 PNS 3 N 3 has given Ph 2 PS 2 N 3 heterocycle in ca. 80% yield. Acid hydrolysis of (R)Ph 2 PNS 3 N 3 derivatives has resulted in the isolation of Ph 2 P(O)OH in all the cases, where R is an amino group.