On the Synthesis of Sulfinyl Cyanides

Free‐Radical Carbocyanation of Olefins

“…The use of a fivefold excess of both reagents to ensure the formation of CF 3 CO 3 H and complete oxidation of 21 led to a mixture of sulfone 20 and sulfinyl cyanide 20′ (Table , entry 1). Compound 20′ could be easily detected by 1 H NMR spectroscopy, which showed two sets of peaks at 4.5 and 4.7 ppm for diastereotopic CH 2 protons . A higher conversion to 20 was obtained by using a 5‐ and then 7.5‐fold excess of reagents and increasing the temperature (Table , entries 2 and 3).…”

Synthetic and Mechanistic Studies on 2,3-Dihydrobenzo[b][1,4]-oxaselenines Formation from Selenocyanates

“…Unexpectedly, the well-known antiparasitic agent WC-9 (compound 50) 34 not only did not afford a cyclized product but also did not produce the corresponding sulfinyl cyanide derivative as depicted for a structurally related derivative (entry 10). 27 The fact that reaction times slowed down when conducted in the presence of (2,2,6,6tetramethylpiperidin-1-yl)oxyl (TEMPO) (1 equiv. ), a radical scavenger, employing selenocyanate 3 as a substrate, suggested that the reaction mechanism involved radical species (entry 11).…”

“…[24][25][26] On the other hand, it was described that on treatment with m-chloroperoxybenzoic acid a thiocyanate moiety can be transformed into a sulfinyl cyanide functional group, as it was the case in such a reaction of benzyl thiocyanate with this oxidizing reagent in refluxing dichloromethane, to yield benzylsulfinyl cyanide (Scheme 1). 27…”