As observed 1,3-dithianes and 1,2-dithiolanes of acetophenones 1a-g were deprotected into their parent ketones with good yields ranging from 54 to 94%. It is of note that, 1,3-dithianes 1b,c, and 1f,g were more cooperative substrates than our model substrate 1a since the deprotection reaction required half quantity of TMSCl/NaI and was achieved at rt under conditions A. Examination of these results also shows that 1,3-dithianes seem easier to deprotect using TMSCl/NaI in CH3CN than their 1,2-dithiolane counterparts (compare 1c and 1d) and that electrondonating groups on the aromatic nucleus allowed more efficient deprotection reactions (compare 1c and 1g). As expected, 1,3-dithianes prepared from aliphatic aryl (cyclic or not) ketones 1h-l reacted well with the TMSCl/NaI combination and furnished ketones 2h-l in good to excellent isolated yields (64 to 91%). The case of dialkyldithiane derivatives was next examined with compounds 1m-p and showed that these compounds were also cooperative substrates as they were rapidly and cleanly deprotected to give the desired ketones 2m-p with satisfactory yields (76 to 95%). When -bromo dithiane 1q was reacted with TMSCl/NaI, acetophenone 2q was obtained indicating that, besides the expected deprotection reaction, a debromination reaction occurred too in agreement with a previous report of Olah. Then, the case of diaryldithianes was examined. Under A classical conditions (TMSCl/NaI 10 equiv, rt, 24 h), we observed that 1,3-dithiane 1r having no H, reacted with TMSCl/NaI to give a mixture composed in almost equal parts of the expected ketone 2r (43%) accompanied by the reduction [Error! Bookmark not defined.] product 1-benzyl-4-methoxybenzene (40%). To avoid the formation of the reduction by-product, we successfully replaced NaI by NaBr, increased the quantity of TMSCl/NaBr and heated the solution at 60 °C for a prolonged time (TLC monitoring). By using these conditions, diarylketones 2r and 2s were then obtained with acceptable yields and without any traces of the reduced diarylmethane by-products. Next, 1,3-dithianes of aldehydes were also studied with compounds 1t and 1u. It is of note that these 1,3-dithianes reacted rapidly under A mild conditions to give the corresponding aldehydes in variable yields. For the deprotection of dithioketals of aldehydes, it is very important to examine carefully the course of the deprotection reaction by TLC monitoring because prolonged reaction times resulted in a severe decrease in yields. Indeed, it has been reported that, at rt, aldehydes reacted rapidly with TMSI to give iodosilyl ethers and diiodoethers. This suggests that, as soon as aldehydes are formed after thioacetal deprotection, they add nucleophilic iodides which may arise from TMSI very slowly generated in the media according to an exchange Finkelstein reaction. To show the interest of this process with respect to other previously reported methods using for examples HgO associated with BF3-Et2O, 2,6-dicarboxy pyridinium chlorochromate (DCPCC) or SbCl5 we have deprotected dithiolanes 1v and 1w by TMSCl/NaI in CH3CN (Scheme 2). The comparison of the yields obtained using the TMSCl/NaI mild association in CH3CN vs toxic oxidizing agent as HgO (86 % vs 65%), DCPCC (93% vs 70%) or SbCl5 (93% vs 77%) supports well that this novel metal-free process is welcome since the yields in desired ketones are significantly higher and the reagents used for the deprotection are inexpensive, not toxic and very easy to handle. A : TMSCl/NaI 10 eq, CH3CN, 24 h, rt. B : TMSCl/NaI 20 eq, CH3CN, 24 h, 60 °C.