Highly scalable photoinduced synthesis of silanols via untraversed pathway for chlorine radical (Cl•) generation

• Published in: Nature communications Vol. 14; no. 1; p. 8173
• Main Authors: Saha, Argha, Ali, Wajid, Werz, Daniel B., Maiti, Debabrata
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 09-12-2023; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/58; 639/638/224/685; 639/638/403/934; 639/638/439/890; Aerobic conditions; Catalysis; Chemical synthesis; Chlorine; Humanities and Social Sciences; Intermediates; multidisciplinary; Photochemicals; Photoredox catalysis; Science; Science (multidisciplinary); Transition metals
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-43286-z

The emergence of visible light-mediated synthetic transformations has transpired as a promising approach to redefine traditional organic synthesis in a sustainable way. In this genre, transition metal-mediated photoredox catalysis has led the way and recreated a plethora of organic transformations. However, the use of photochemical energy solely to initiate the reaction is underexplored. With the direct utilization of photochemical energy herein, we have established a general and practical protocol for the synthesis of diversely functionalized organosilanols, silanediols, and polymeric siloxanol engaging a wide spectrum of hydrosilanes under ambient reaction conditions. Streamlined synthesis of bio-active silanols via late-stage functionalization underscores the importance of this sustainable protocol. Interestingly, this work also reveals photoinduced non-classical chlorine radical (Cl
•
) generation from a readily available chlorinated solvent under aerobic conditions. The intriguing factors of the proposed mechanism involving chlorine and silyl radicals as intermediates were supported by a series of mechanistic investigations.
Contrary to photocatalysis, the use of photochemical energy solely to initiate reactions is underexplored. Here, the authors demonstrate light initiated synthesis of functionalized organosilanols, silanediols, and polymeric siloxanol under ambient reaction conditions.