Next, as dithioacetals, the regeneration of carbonyl compounds from nitrogen-derivatives as hydrazones, N-tosylhydrazones, ketimines and oximes required most of the time harsh reaction conditions including oxidative or reducing process, acidic or alkaline media, expensive reagents or hazardous experimental protocols. In order to find a milder process, we next examined if the TMSCl/NaI combination in CH3CN process could be applied successfully to these robust nitrogen substrates. In Scheme 3 were presented the results of the regeneration of carbonyl functions of 6, N-tosylhydrazone 7, Nbenzylimine 8, ketimine 9 and diphenylmethanone oxime 10, using TMSCl/NaI in CH3CN. We were pleased to observe that the TMSCl/NaI combination in CH3CN was able to transform imines and hydrazones into ketones with good yields (90 to 100%) as well as N-tosylhydrazone 7 which required the use of stronger reaction conditions. On the contrary, imine 8 and ketimine 9 were easily transformed into their ketones with high yields using the TMSCl/NaI association in CH3CN at rt. When diphenylmethanone oxime 10 was reacted with the TMSCl/NaI association (10 eq), we isolated, after 24 h of reaction achieved at rt, 4-methoxy-N-(4methoxyphenyl)benzamide 11 in a good yield (84%) accompanied by only 4 % of the bis(4methoxyphenyl)methanone 2r. The scope of this interesting Beckmann rearrangement, using the TMSCl/NaI combination, is currently under investigation in our lab with a range of oxime substrates. Scheme 4. Plausible mechanism A plausible reaction mechanism is indicated in (Scheme 4). First, CH3CN activates the TMSCl/NaI association as mentioned previously by Olah [Error! Bookmark not defined.] to promote intermediate I and II after halide exchange in the presence of NaI. Then, II reacts with a sulfur atom of dithiolane 1c to give a sulfonium species of type III. Further assistance from the neighboring dithiane sulfur atom possibly leads to a fragmented sulfonium intermediate IV which added H2O (from reagents, CH3CN or during hydrolysis) to promote hemithioketal V which is then activated into a sulfonium intermediate VI (having or not H. With no H as in 1r or 1s, VI finally rearranges into the desired ketone 2d. For dithiolanes prepared from enolizable ketones as 1c, the same (a) pathway could be followed but it is also reasonable to consider an additional pathway (b) in which an iodide deprotonates intermediate VI to furnish an enol species which tautomerizes into ketone 2d. Since dithioacetals having H can evolve according to two different pathways, this can explain that these entities are easier to deprotect than diarylthioketals counterparts. It is of note that a similar mechanism has been previously proposed by Nicolaou for the deprotection of S,S-acetals and ketals using IBX.