A useful synthesis of chiral sulfonyl cyanides: (1S,2S,5R)-2-isopropyl-5-methylcyclohexanesulfonyl cyanide

Free‐Radical Carbocyanation of Olefins

“…An initiation step should generatee lectrophilicr adical I,t he addition of Reactiono ft he latter with 20 would give the product along with an alkylsulfonylr esidue (EtO 2 CCH 2 SO 2 ), a-scission of which (andl oss of SO 2 )w ould regenerate I and thus sustain the radical chain. [27] Preliminary attempts to oxidize 21 with oxone, but also MnO 2 or KMnO 4 /MnO 2 ,f ailed to afford satisfactory yields of the desired sulfonyl cyanide 20,a nd led insteadt ot he formation of the corresponding carbamothioate( EtO 2 CCH 2 S(C=O)NH 2 ), throughh ydrolysis of 21 (see SupportingI nformation). [25] This approach is usually limited to aryl thiocyanates, [26] and only one report mentioned ag ood yield for oxidation of an alkyl thiocyanate with meta-chloroperoxybenzoic acid (m-CPBA).…”

Thiocyanation of Pyrazoles Using KSCN/K2S2O8 Combination

“…CH 3 CN, 1,2-dichloroethane (DCE) and DMSO (entries [6][7][8][9][10][11], and DMSO provided the highest yield of the desired product 3a of 96% (entry 11). Under the optimized conditions (entry 11), the source of thiocyanate was next examined and KSCN gave the optimal results (entries 11-13).…”

“…It was found that only trace amounts of 3a were observed when H 2 O, 1,tetrahydrofuran (THF), N,Ndimethylformamide (DMF) and CH 2 Cl 2 were employed as the solvents (entries [1][2][3][4][5]. Better results were observed when the reactions were performed in EtOH, CH 3 OH, EtOAc, SYNOPEN2 5 0 9 -9 3 9 6 Georg Thieme Verlag Stuttgart · New York 2018, 2, [6][7][8][9][10][11][12][13][14][15][16] paper en T. Songsichan et al…”

“…Among various sulfur-containing substances, thiocyanate derivatives, particularly aryl-and heteroaryl thiocyanates, are an important class of compounds exhibiting pharmacological potential 2 and serving as versatile synthetic precursors for the synthesis of various organosulfur derivatives such as thiols, 3 thioethers, 4 thiocarbamates, 5 thioesters, 6 disulfides, 7 sulfonic acids, 6 sulfonyl chlorides, 8 and sulfonyl cyanides. 9 A number of synthetic routes are available for the synthesis of aryl-and heteroaryl thiocyanates including coupling of diazonium salts with metal thiocyanates under Sandmeyer type conditions, 10 cyanation of organosulfur and organometallic compounds, 11 metal-catalyzed coupling reaction of arylboronic acids with trimethylsilylisothiocyanate (TMSNCS) or aryl halides with thiocyanate salts 12 and the direct thiocyanation of C-H bonds with thiocyanates. 13 Pyrazoles and their derivatives have attracted increasing interest in the fields of medicine and pharmacology because of their interesting biological properties including antifungal, 14 antibacterial, 15 anticancer, 16 anti-inflammatory, 17 antiviral, 18 antioxidant, 19 cytotoxic, 20 antihypertensive, 21 antitubercular, 22 analgesic, 23 antipyretic, 24 anticonvulsant, 25 and A3 adenosine receptor antagonistic activities.…”

“…Various reaction parameters including solvent, thiocyanate source, oxidizing agent, reagent stoichiometry, temperature and reaction time were screened and the results are summarized in Table 1. First, various solvents were evaluated using 1-methyl-3,5-diphenyl-1H-pyrazole (1a; 0.5 mmol), KSCN (2a; 2 equiv) and K 2 S 2 O 8 (1.5 equiv) at room temperature for 24 h (entries [1][2][3][4][5][6][7][8][9][10][11]. It was found that only trace amounts of 3a were observed when H 2 O, 1,tetrahydrofuran (THF), N,Ndimethylformamide (DMF) and CH 2 Cl 2 were employed as the solvents (entries [1][2][3][4][5].…”