Phosphinylmethyl Isocyanides

Abstract

Compound (3) quickly exchanges deuterium with deuterated solvents, the NMR signal at -10.5 ppm disappearing.A compound of m.p. 195 "C analogous to (3). and to which we ascribe structure (4), was obtained from 2,6-bis-(4methoxyphenyl)-4-phenylphosp horin.(4), UV: Amax = 240 nm, E = 8 . 3~ lo4 (in methanol); NMR: quartet at -3.3 ppm (2 benzyl-H), JP-CH = 28 Hz, singlet at -3.72 (6 H, 0-CH3); band complex at -7.5 to -6.5 (30 H (aromatic and olefinic); Molecular weight (mass spectrometric) = 820 (* 5); further fragments at mle = 400 and 384, of which the second peak is to be ascribed to 2,6-bis44methoxyphenyl)-4-phenylphosphorin. JHa/Hb= 5 HZ; singlet at -3.70 ppm (6 H,O-CH3), 7 6 H 5 d6H5

Multicomponent Reactions with Isocyanides

“…In this reaction, water formally reacts as the acid component. [83,160,168,169] An alternative and complementary method for the preparation of a-amino amides like 181 is the reaction of isocyanides with an amine, an oxo compound, and CO 2 acid (180) formed intermediately is hydrolyzed after expansion of the pressure reactor. [170] Whereas hydrogen sulfide can only be converted to aamino thioamides as the acid component in the shape of thiosulfate, hydrogen selenide reacts smoothly to the a-amino selenoamides.…”

Multikomponentenreaktionen mit Isocyaniden

“…Dabei fungiert Wasser formal als Säurekomponente. [83,160,168,169] Während sich Schwefelwasserstoff nur in Form von Thiosulfat als Säurekomponente zu a-Aminothioamiden umsetzen lässt, reagiert Selenwasserstoff glatt zu den a-Aminoselenoamiden. [102] Alkohole liegen in CO 2 -Atmosphäre im Gleichgewicht mit ihren Monoalkylkohlensäureestern vor.…”

Acid-Free, Aminoborane-Mediated Ugi-Type Reaction Leading to General Utilization of Secondary Amines

“…This mechanism-based requirement makes it difficult to use secondary amines as the amine component in the Ugi reaction, although the use of secondary amines has partly been achieved by the use of excess dimethylamines or by the use of secondary amines that carry additional functional groups, such as OH and NHR groups, which serve as intramolecular acyl group receptors . Secondary amines also took part in a certain Ugi-type reaction, where formaldehyde was used as a highly reactive carbonyl component . Because α-dialkylamino acid derivatives, including those with cyclic amino groups, attract much attention as potential drugs or biologically active substances, it is highly desirable to develop entirely new reaction conditions that allow utilization of secondary amines.…”