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Rück-Braun, K.; Freysoldt, T., Science of Synthesis, (2007) 35, 272.
The ring opening of thiiranes 5 with acyl chlorides leads to S-chloroalkyl sulfinothioates 6 and 7. The reaction is mediated either by cobalt(II) chloride[4] as catalyst or by addition of tetrabutylammonium chloride or bromide or crown ether complexes as additives.[5,6] Monosubstituted as well as bicyclic oxiranes can be opened by this method. The cobalt-catalyzed reaction leads to mixtures of the regioisomers, while the reaction in the presence of an additive yields chlorothioates 6 regioselectively (Scheme 3).
Meeeee 8 Meeeeeeee ee M-Meeeeeeeeee Meeeeeeeeeeeeee[8–8]
M8 | M8 | M8 | Meeeee | Meeee (8/8) | Meeee (%) | Mee |
---|---|---|---|---|---|---|
MM8MeMe | M | Me | M | 8:8 | 88 | [8] |
MM8Me | M | Me | M | 8:8 | 88 | [8] |
Me | M | Me | M | 8:88 | 88 | [8] |
(MM8)8 | Me | M | – | 88 | [8] | |
MM8MMe | M | Me | M ee M | 8:8 | 88 | [8,8] |
MM8MMe | M | Me | M | 8:8 | 88 | [8,8] |
MM8MMe | M | Me | M | 8:8 | 888 | [8,8] |
Meeeeeeeeeee Meeeeeeee
M-(8-Meeeee-8-eeeeeeeeeee) Meeeeeeeeeeee (8, M8 = Me; M8 = M; M8 = Me); Meeeeee Meeeeeeee:[8]
MMMMMMM: Meeeee(MM) eeeeeeee ee eeeee eee eee eeeee eeeeee. Meeeee eeeeee eeeeeeeeeee eeeeee ee eeeee eeeeee eeeeeeee eee eeeeeee.
Meeeee M: Meeee MeMe8 (8.8 ee, 8.88 eeee) eee eeeee ee e eeee ee 8-eeeeeeeeeeeeee (8, M8 = Me; M8 = M; 888 ee, e eeee) eee MeMe (8.8–8 eeee) ee MM8Me8 (8 eM). Mee eeeeeee eee eeeeeee ee ee eee 88 eee. Meeee eeeeeeeeee ee eee eeeeeeee (MM ee MMM eeeeeeeeee), eee eeeeeee eee eeeeeeeee eeee Me8M (88 eM) eee eeeeee eeee M8M (88 eM), eee eee eeeeeee eeeee eee eeeee (Me8MM8). Mee eeeeeee eee eeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee ee e eeeee eeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 8:8); eeeee: 888 ee (88%); 8M MMM (MMMe8, δ): 8.8–8.8 (e, 8M), 8.8 (e, 8M), 8.8 (ee, 8M), 8.8 (e, 8M).
References
[4] | Meeeeeee, M.; Meeeeeeeeee, M.; Meeeee, M. M., Meeee. Meeeee., (8888) 88, 8888. |
[5] | Meeeeeee, M.; Meeeee, M.; Meeeeeeee, M., Meeeeeeeeeeeee, (8888) 88, 8888. |
[6] | Meeeeeee, M.; Meeeee, M.; Meeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8, 888.
- 8.Meeeee-Meee, (8888) M 8, 88.
- 8.Meeeee-Meee, (8888) M 88-8, 8888.
- 8.Meeeee-Meee, (8888) M 8-8, 888.