Beilstein Journal of Organic Chemistry p. 2897 - 2906 (2018)
Update date:2022-08-04
Topics:
Lozovskiy, Stanislav V.
Ivanov, Alexander Yu.
Khoroshilova, Olesya V.
Vasilyev, Aleksander V.
In strong Br?nsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.
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Doi:10.1016/S0008-6215(00)80547-9
(1982)Doi:10.1016/S0040-4039(01)80480-9
(1989)Doi:10.1039/c39950000849
(1995)Doi:10.1007/s00706-004-0195-5
(2004)Doi:10.1016/j.bmcl.2006.12.038
(2007)Doi:10.1021/jm00355a019
(1983)