Pseudohalogen Chemistry. Part Iv. Heterolytic Addition of Thiocyanogen to Alkenes

One-pot anodic thiocyanation and isothiocyanation of alkenes

“…2,3-Dimethyl-2-isothiocyanato-3-thiocyanatobutane (1) [15]. IR: a sharp peak of thiocyanate group at 2152 cm -1 , a broad peak of isothicoyanate group at 2067 cm -1 ; 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 1-Isothiocyanato-1-methyl-2-thiocyanatocyclohexane (one diastereoisomer) (11) [17].…”

“…for C 8 H 12 N 2 S 2 +H + : 201.0515 and C 8 H 12 N 2 S 2 +Na + : 223.0334; found 201.0515 and 223.0335, respectively.2,3-Dimethyl-2,3-dithiocyanatobutane (2)[15]. IR: a sharp peak of thiocyanate group at 2152 cm -1 ; 1 H-NMR (in CDCl 3 , 400MHz): δ=1.76 (s, 12H);13 C-NMR (in CDCl 3 , 400MHz): IR: a sharp peak of thiocyanate group at 2152 cm -1 , a broad peak of hydroxyl group at 3452 cm -1 ; 1 H-NMR (in CDCl 3 , 400MHz): δ=1.38 (s, 6H), δ=1.61 (s, 6H); 13 C-NMR (in CDCl 3 , 400MHz): δ=25.85, 26.07, 64.86, 75.65, 113.12; GC-MS (m/z) (%): 159 (M + ), 116, 101, 83, 74 (100), 59, 41; MS (MALDI-TOF): m/z calc.…”

α-Amino Radical-Mediated Diverse Difunctionalization of Alkenes: Construction of C–C, C–N, and C–S Bonds

“…The formation of the isothiocyanate products may be due to steric effects in the capture of SCN at sulfur versus nitrogen. 19 In addition to 4n and 4o, we also obtained alkene byproducts 4n′ and 4o′ (18% and 14%, respectively) which suggest the involvement of benzylic carbocations. 1-Indene underwent dichloromethylthiocyanation with moderate yield but low diastereoselectivity (4p).…”

“…Though isomerization between thiocyanates and isothiocyanates had been reported, we did not detect initial thiocyanate products when the reactions were monitored by NMR spectroscopy. The formation of the isothiocyanate products may be due to steric effects in the capture of SCN at sulfur versus nitrogen . In addition to 4n and 4o , we also obtained alkene byproducts 4n′ and 4o′ (18% and 14%, respectively) which suggest the involvement of benzylic carbocations.…”