Harnessing attractive noncovalent interactions (NCIs) between substrates and catalysts has emerged as an effective strategy in homogeneous catalysis. The long-range nature and conformational flexibility of NCIs enable catalysts to adapt to structural changes in substrates, while maintaining remote control over selectivity. This approach is applicable to both site-selective and stereoselective reactions of arenes, offering new opportunities for generality-oriented catalysis.

Abstract

Remote control of the site-selectivity and stereoselectivity offers new opportunities in accessing novel structures. Covalent templating strategies require an individual rigid tether that matches the geometry of a specific substrate. Recently, methods have been developed to steer the catalytic centers by engaging noncovalent interactions (NCIs) between the substrates and catalysts. Owing to the extended effective distance and flexible directionality of NCIs, it has been discovered that such approaches are adaptable to structural changes of the substrates while preserving the preorganization between substrates and catalysts. This review summarizes the innovation and application of remote control of site-/stereo-selectivity for reactions of arenes featuring NCIs-enabled substrate adaptability.