On the Effect of Backbone Modifications in 3,3‐Dimethyl‐1‐(trifluoromethyl)‐3H‐1λ³,2‐benziodaoxole

Abstract

We report on the effect of small side‐chain modifications to the structure of 3,3‐dimethyl‐1‐(trifluoromethyl)‐3H‐1λ3,2‐benziodaoxole (1b) on its reactivity, as expressed by the initial rate v0 in a model reaction, and show how the latter can be successfully correlated to an easily determined physical parameter p, a 13C NMR chemical shift. The relationship v0 ~ p is already present in the simplest starting material devoid of the hypervalent bond and the iodine core and, therefore, presents an interesting approach towards the future scaffold‐optimization of this class of reagents.

Organohypervalent heterocycles

“…A wide range of cyclic trifluoromethyl-substituted iodanes has been prepared and their structures and reactivity in trifluoromethylation reactions reported. [575][576][577][578][579][580][581] Cyclic trifluoromethyliodane reagents are comparatively stable and safe to handle compared to their corresponding acyclic compounds, which are, in general, unstable due to the weak C-I bond between the carbon atom of the CF 3 group and the hypervalent iodine center. The reactions of these reagents with alkene or alkyne substrates can give the addition of trifluoromethyl groups, as well as trifluoromethylation followed by cyclization.…”

Recent Progress in Synthetic Applications of Cyclic Hypervalent Iodine(III) Reagents

“…Numerous cyclic trifluoromethyl-substituted hypervalent iodine compounds with different substituents in the ring have been prepared and their structures and reactivity in trifluoromethylation reactions have been reported. [83][84][85][86][87][88][89] Furthermore, the complexes of these reagents with various acids and organometallic compounds were prepared and investigated. [90][91][92][93][94][95] Xue and Cheng reported the trifluoromethyl cation donating capacity of trifluoromethylbenziodoxoles with various substituents, in which the correlation of reactivity with the nature of substituents was investigated as well as the enhancement of trifluoromethylation capacity by additives.…”

“…Recently, several trifluoromethylbenziodoxole reagents have also become commercially available from chemical companies. Numerous cyclic trifluoromethyl‐substituted hypervalent iodine compounds with different substituents in the ring have been prepared and their structures and reactivity in trifluoromethylation reactions have been reported [83–89] . Furthermore, the complexes of these reagents with various acids and organometallic compounds were prepared and investigated [90–95] .…”

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

“…Alternatively, a series of geminal ‐methyl,alkyl derivatives was also synthesized from bromobenzene 22 and aliphatic ketones ( Scheme 3 ,c ) [25] . Phenyllithium was formed by transmetalation and added to a series of aliphatic ketones to form benzyl alcohol derivatives.…”