Driving Innovations in Organic Synthesis and Organometallic Chemistry Based on Exploration of Solution and Solid-State Reactions
Dr. Ito has made significant contributions to organic synthesis and material science by developing novel methods for organoboron and organosilicon compound synthesis, pioneering functional materials responsive to mechanical stimuli, and advancing high-efficiency mechanochemical organic synthesis.
1. Synthetic Methods for Organoboron and Organosilicon Compounds
In 2000, Ito first developed a copper(I)-catalyzed borylation reaction using diborons, which became a foundation for innovative synthetic approaches to organoboron compounds. His research gained global recognition, earning The Chemical Society of Japan Award for Creative Work in 2013. Over the following decade, he further refined his methods, incorporating computational chemistry to design asymmetric ligands, leading to highly efficient asymmetric reactions, including asymmetric Markovnikov-type borylation of terminal alkenes, asymmetric borylation of benzylic halides, and improvement in enantioconvergent reactions and stereoselectivity reversal in asymmetric borylation processes. He also developed efficient synthesis of amino acid-like acylboranes, and stereoselective multi-substituted allylboron compounds. His work extended beyond copper(I)-catalysis to discover novel reactions involving stable B-O bonds and alkyne intermediates. In organosilicon chemistry, Ito achieved groundbreaking results by developing catalytic methods for synthesizing sterically hindered and functionalized silylboranes. He achieved the world's first synthesis of optically active silylboranes, activated these compounds to generate versatile silicon nucleophiles, and proposed iterative coupling methods for constructing complex oligosilanes. This revolutionized organosilicon chemistry and opened new pathways for advanced material synthesis.
2. Mechanically Responsive Crystalline Materials
Ito's exploration of organometallic crystals responsive to mechanical stimuli began in 2008, with his report on gold isocyanide complexes that exhibit changes in crystal structure and luminescence upon mechanical stimulation. He further expanded this research by designing gold isocyanide complexes with diverse luminescent responses to mechanical stimuli, significantly advancing the potential applications of such materials. Through the use of crystal chirality and solvent inclusion, he designed systems capable of reversible single-crystal-to-single-crystal phase transitions via mechanical stress and solvent exposure. He also discovered "jumping crystals" that respond to light irradiation and developed "dancing crystals," which include ferroelasticity with thermal phase transitions. These materials demonstrated entirely new perspectives in the design and application of crystalline materials responsive to external stimuli, broadening the horizons of functional materials science.
3. Highly Efficient Mechanochemical Organic Synthesis
Inspired by his previous work on mechanically responsive crystals, Ito began exploring mechanochemistry as a means of advancing organic synthesis. He demonstrated that many traditional solvent-based organic reactions could be performed more rapidly, with less waste, by using ball-milling techniques and appropriate reaction designs. His work opened new possibilities in green chemistry and sustainable synthesis. In cross-coupling reactions such as Buchwald-Hartwig and Suzuki-Miyaura, Ito discovered methods to prevent catalyst deactivation and improve reaction efficiency under mechanochemical conditions. He proposed selective cross-coupling strategies based on differences in solid-liquid reactivity and designed catalysts optimized for mechanochemical synthesis. These developments provided a novel direction for this field. He addressed challenges associated with poorly soluble substrates by employing high-temperature mechanochemical methods, enabling efficient transformations of otherwise intractable compounds. His efforts significantly contributed to overcoming key obstacles in organic synthesis, particularly for insoluble materials. Further extending the applications of mechanochemistry, Ito synthesized organometallic compounds, including palladium and iridium complexes, and achieved the first mechanochemical synthesis of Grignard reagents, organocalcium, organobarium, and organolithium compounds. These achievements were previously considered highly challenging. He also developed a simplified and faster Birch reduction, demonstrating the potential of mechanochemical approaches in tackling traditionally difficult reactions. Ito also introduced a groundbreaking concept in mechanochemical synthesis: mechanoredox reactions. By utilizing the piezoelectric potential of materials as an energy source, he developed reactions that can mimic photoredox methods. This innovation further expanded the boundaries of green chemistry and demonstrated the versatility of mechanical forces in driving chemical reactions. He also utilized mechanoradicals, generated through ball mill-induced polymer backbone cleavage, for material synthesis and as initiators for radical-based reactions. These novel approaches exemplified his ability to integrate mechanical energy into synthetic chemistry, introducing transformative concepts to the field.
Ito's contributions extend beyond individual discoveries, representing a paradigm shift in organic synthesis and material science. His work on reaction design under solution and mechanochemical conditions and functional crystalline materials has not only expanded the capabilities of organic and organometallic chemistry but also paved the way for sustainable and innovative approaches to chemical industry. These achievements have been recognized as groundbreaking, earning him the prestigious Chemical Society of Japan Award.