Non-reductive decyanation reactions of disubstituted malononitrile derivatives promoted by NaHMDS

C–C Bond Breaking in Addition–Elimination Reactions on Nitriles

“…This pathway could be significant for the reaction of organolithiums with 1‐cyanotetrahydronaphthalene derivatives (instead of the pathway through a four center transition state) or the reaction of Grignard reagents with triarylacetonitriles (instead of an electron transfer mechanism) . Finally, even if the potassium case was not considered in our work, the investigation of the addition‐elimination mechanism may bring a fresh perspective to KHMDS mediated S N Ar‐decyanation reactions starting from dibenzothiophene dioxides and arylacetonitriles …”

Amination of Carbenium Ions Generated by Directed Protonolysis of Cyclopropane

“…The crude product was purified by column chromatography (eluent hexanes/EtOAc 8:1, R f = 0.55) to afford nitrile 23 (537 mg, 69%) as a colorless oil. This compound is known …”

“…2,2,2-Trichloro-N-(2-cyclohexylideneethyl)acetamide (20). 14 Trichloroacetyl chloride (726 mg, 3.99 mmol) was added dropwise to a cooled (0 °C) solution of amine 19 (500 mg, 3.99 mmol) and Et 3 N (1.21 g, 11.97 mmol) in CH 2 Cl 2 (5 mL), and reaction mixture was stirred for 4 h. The reaction mixture was diluted with 1 M aq HCl and stirred for 5 min.…”

“…This compound is known. 20 Ethyl (2-Cyclohexylidenepropyl)carbamate (24). 14 Carbamate 24 was prepared by an analogy to carbamate 17a from nitrile 23 (497 mg, 3.67 mmol), LiAlH 4 (460 mg, 12.13 mmol), AlCl 3 (515 mg, 3.85 mmol), and ethyl chloroformate (1.20 g, 11.02 mmol) in Et 2 O (50 mL).…”