Recent Advances in the Functionalizations of the Upper Rims of Thiacalix[4]arenes. A Review

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Abstract
The chemistry of the thiacalixarenes is very recent compared to that of similar calixarenes. Several papers have recently reported interesting progress in the chemistry of thiacalixarenes. Until recently most of the reactions concerned the substitutions of the lower rims while only very few were dealing with the upper rims. Indeed it was shown that the macrocycles often behave in a very different way compared to the similar calixarenes, and the well-known reactions such as nitration, bromination or formylation could not be directly transposed to the thiacalixarenes. However many important intermediates for upper-rim substitution were recently reported and are resumed in this paper together with further functionalizations of the upper rims and potential developments in the chemistry and applications of thiacalixarenes. A review with 40 references.