ChemInform Abstract: Selected Reactions of Diethyl (E)‐1‐(Bromomethyl)‐2‐cyanovinylphosphonate with Secondary and Tertiary Amines.

Abstract

Selected Reactions of Diethyl (E)-1-(Bromomethyl)-2-cyanovinylphosphonate with Secondary and Tertiary Amines. -The reaction of phosphonate (I) with less bulky secondary amines leads to phosphonates of type (III)/(IV) after substitution and rearrangement. More bulky secondary amines afford the normal substitution products of type (V). The reaction with tertiary amines affords phosphonate (VII). -(FRAY, A.; BEN KRAIEM, J.; AMRI*, H.; Heteroat. Chem. 24 (2013) 6, 460-465, http://dx.doi.org/10.1002/hc.21112 ; Fac. Sci. Tunis, Univ. El-Manar, 2092 El Manar, Tunis, Tunisia; Eng.) -M. Bohle 15-205

Organocatalyzed synthesis of functionalized vinylphosphonates in water

“…Thus, the use of sodium azide led to diethyl azidomethyl vinylphosphonate 13 (entry 1) in 89% yield, whereas sodium sulfinate (entry 2), potassium thioacetate (entry 3), sodium methanethiosulfonate (entry 4), and potassium cyanide (entry 5) also gave the corresponding compounds 14 ‐ 17 with satisfactory yields.…”

Selected Reactions of Diethyl (E)‐1‐(bromomethyl)‐2‐cyanovinylphosphonate with Secondary and Tertiary Amines

“…We have recently reported a highly stereoselective synthesis of diethyl ( E )‐1‐(bromomethyl)‐2‐cyanovinylphosphonate 1 , using an unusual successive S N 2′‐S N 2′ reaction of 1,4‐diazabicyclo[2.2.2]octane (DABCO) then KCN on available diethyl 1‐(acethoxymethyl) vinylphosphonate, followed by a radical brominating reaction of the resulting β‐cyanophosphonate E as shown in Scheme .…”

“…It was considered as the most successful pathway for carbon–heteroatom bond formation . Considering the importance of CN bonding creation in organic synthesis and in connection with our research projects aimed to develop new routes to α‐functional allylamines , we report herein the behavior of diethyl ( E )‐1‐(bromomethyl)‐2‐cyanovinylphosphonate 1 as a powerful Michael acceptor , toward secondary and tertiary amines as a source of N ‐nucleophilic reagents.…”