α,β-Aziridinylphosphonates by lithium amide-induced phosphonyl migration from nitrogen to carbon in terminal aziridines

Lithiation-induced migrations from nitrogen to carbon in terminal aziridines.

Straightforward synthesis of 1-alkyl-2-(trifluoromethyl)aziridines starting from 1,1,1-trifluoroacetone.

An efficient and straightforward approach towards the synthesis of 1-alkyl-2-(trifluoromethyl)aziridines starting from 1,1,1-trifluoroacetone via imination, α-chlorination, hydride reduction and ring closure was developed. In addition, novel primary β-iodo amines were obtained by regioselective ring opening of these 2-(trifluoromethyl)aziridines using alkyl iodides, and their synthetic potentia...

Highly regioselective synthesis of functionalized aminonitriles starting from 2-(ω-cyanoalkyl)aziridines

1-arylmethyl-2-(bromomethyl)aziridines were transformed into the corresponding 2(cyanomethyl)aziridines and 2-(2-cyanoethyl)aziridines upon treatment with potassium cyanide in DMSO and α-lithiated trimethylsilylacetonitrile in THF, respectively. Further elaboration of 1-arylmethyl-2-(cyanomethyl)aziridines afforded 4-amino-2-butenenitriles, 3,4diaminobutanenitriles and 2-aminocyclopropanecarbon...

Asymmetric synthesis of α-alkenyl homoallylic primary amines via 1,2-addition of Grignard reagent to α,β-unsaturated phosphonyl imines.

A series of chiral N-phosphonyl protected α-alkenyl homoallylic primary amines were synthesized by asymmetric addition of allylmagnesium bromide Grignard reagent towards chiral α,β-unsaturated imines. Only 1,2-adduct was obtained for all the imines with good yields and excellent diastereoselectivities. The chiral auxiliary could be easily removed under simple conditions, giving free multiple fu...

Intriguing roles of reactive intermediates in dissociation chemistry of N-phenylcinnamides.

In mass spectrometry of protonated N-phenylcinnamides, the carbonyl oxygen is the thermodynamically most favorable protonation site and the added proton is initially localized on it. Upon collisional activation, the proton transfers from the carbonyl oxygen to the dissociative protonation site at the amide nitrogen atom or the α-carbon atom, leading to the formation of important reactive interm...