AI Article Synopsis
- Chalcogen bonding is a type of noncovalent interaction involving electrophilic chalcogen elements, similar to hydrogen and halogen bonding, and this research explores its application in organocatalysis using selenium-based compounds.
- Cationic bifunctionalized organoselenium compounds effectively activate the carbon-chlorine bond in 1-chloroisochroman, with benzimidazolium structures proving more effective than imidazolium counterparts.
- The study demonstrated that syn-isomers of these catalysts exhibit significantly higher activity due to bidentate coordination, achieving a tenfold increase in reaction rate due to chalcogen bonding compared to non-selenated alternatives.
Article Abstract
Chalcogen bonding is a noncovalent interaction based on electrophilic chalcogen substituents, which shares many similarities with the more well-known hydrogen and halogen bonding. Herein, the first application of selenium-based chalcogen bond donors in organocatalysis is described. Cationic bifunctionalized organoselenium compounds activate the carbon-chlorine bond of 1-chloroisochroman in a benchmark reaction. While imidazolium-based derivatives showed no noticeable activation, benzimidazolium backbones yielded potent catalysts. In all cases, syn-isomers were markedly more active, presumably due to bidentate coordination, which was confirmed by DFT calculations. Comparison experiments with the corresponding non-selenated as well as the non-cationic reference compounds clearly indicate that the catalytic activity can be ascribed to chalcogen bonding. The rate acceleration by the catalyst-compared to the non-selenated derivative-was about 10 fold.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5725716 | PMC |
| http://dx.doi.org/10.1002/chem.201704502 | DOI Listing |
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