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Catalysis with chalcogen bonds: neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength.

ABSTRACT: The benzodiselenazoles (BDS) introduced in this report fulfill, for the first time, all the prerequisites for non-covalent high-precision chalcogen-bonding catalysis in the focal point of conformationally immobilized σ holes on strong selenium donors in a neutral scaffold. Rational bite-angle adjustment to the long Se-C bonds was the key for BDS design. For the unprecedented BDS motif, synthesis of 12 analogs from o-xylene, crystal structure, σ hole variation strategies, optoelectronic properties, theoretical and experimental anion binding as well as catalytic activity are reported. Chloride binding increases with the depth of the σ holes down to K_D = 11 μM in THF. Catalytic activities follow the same trend and culminate in rate enhancements for transfer hydrogenation of quinolines beyond 100 000.

SUBMITTER: Benz S

PROVIDER: S-EPMC5855965 | biostudies-literature | 2017 Dec

REPOSITORIES: biostudies-literature

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Catalysis with chalcogen bonds: neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength.

Benz Sebastian S Mareda Jiri J Besnard Céline C Sakai Naomi N Matile Stefan S

Chemical science 20171016 12

The benzodiselenazoles (BDS) introduced in this report fulfill, for the first time, all the prerequisites for non-covalent high-precision chalcogen-bonding catalysis in the focal point of conformationally immobilized σ holes on strong selenium donors in a neutral scaffold. Rational bite-angle adjustment to the long Se-C bonds was the key for BDS design. For the unprecedented BDS motif, synthesis of 12 analogs from <i>o</i>-xylene, crystal structure, σ hole variation strategies, optoelectronic pr ...[more]

PMID: 29568463

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