Phenolysis and benzenethiolysis reactions of carbonyl and thiocarbonyl compounds from the perspective of the HSAB principle

Pavez, Paulina; Herrera, Bárbara; Castro, Enrique A.; Santos, José G.; Toro–Labbé, Alejandro

doi:10.1016/j.theochem.2007.02.023

Cited by 3 publications

(2 citation statements)

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“…Although several disconnections evoking various sulfur sources might be proposed to access such a tetravalent construct, we were particular drawn to developing a method exploiting as a key step the thiolcarbonate (RSC(O)OR) function. 3 This particular functional motif has rarely been identified in natural compounds, 4 but its presence in certain antimalarial compounds appears to lead to an enhancement in these analogues of the antiplasmodium effect. 5 The thiolcarbonate function has had wider use as an intermediate in organic chemistry where it has been encountered as an aglycone in glycosyl donors 6 used in intramolecular S-glycosylations assisted by palladium catalysis, 7 as a spacer group fragment, 8 and in a route to carbamates.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In a project related to the investigation of bacterial adhesion events we required a convenient synthesis of a number of sugar-derived unsymmetrical thioethers and in particularly of sugar-functionalized thiacalix[4]erene such as the tetravalent glucose analogue described herein (Figure ). Although several disconnections evoking various sulfur sources might be proposed to access such a tetravalent construct, we were particular drawn to developing a method exploiting as a key step the thiolcarbonate (RSC(O)OR) function . This particular functional motif has rarely been identified in natural compounds, but its presence in certain antimalarial compounds appears to lead to an enhancement in these analogues of the antiplasmodium effect .…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Unsymmetrical Thioethers Using an Uncommon Base-Triggered 1,5-Thiol Transfer Reaction of 1-Bromo-2-alkylthiolcarbonates

et al. 2014

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Described herein is a convenient, odorless, metal-free, one-pot strategy for the synthesis of unsymmetrical thioethers. The key step in this new strategy is a base-catalyzed 1,5-thiol transfer reaction via a pseudointramolecular mechanism of a 1-bromo-2-alkylthiolcarbonate, which is itself obtained through a straightforward microwave-assisted thioalkylation of a 1,2-cyclic-thionocarbonate precursor with an appropriate alkyl bromide. The starting 1,2-cyclic-thionocarbonates are easily obtained from the corresponding diols. When a propargylthiolcarbonate constitutes the key alkylthiolcarbonate 1,5-shift precursor, a copper-mediated dipolar cycloaddition reaction ("click") with azide partners is rendered possible. This increases the versatility of the approach, as a very large variety of complex triazole-tethered substrates can potentially be integrated into the target unsymmetrical thioether final products. As an example of the scope of the reaction, four 1,5-shift reactions have been triggered simultaneously from a sugar-derived tetrathiolcarbonate precursor using base catalysis, to allow four 6-thioglucose moieties to be installed (78% yield for each sugar unit) onto a 1,3-alternate thiacalix[4]arene scaffold in a one-pot transformation.

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