Nickel‐Catalyzed Reductive Protocol to Access Silacyclobutanes with Unprecedented Functional Group Tolerance

• Published in: Angewandte Chemie International Edition 2024-11, Vol.63 (47), p.e202407773-n/a
• Main Authors: Yang, Ling‐yun, Qin, Ying, Zhao, Zhihan, Zhao, Dongbing
• Format: Article
• Language: English
• Subjects: catalysis; Chemical reactions; Chemical synthesis; Chlorosilanes; Coupling; Cycloaddition; C−Si coupling; Functional groups; Halides; Lithium; nickel; Reagents; reductive coupling; silacyclobutanes; Substitution reactions; Transition metals
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202407773

While significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions of 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we present a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted silacyclobutanes with aryl or vinyl halides and pseudohalides, thereby obviating the need for organometallic reagents. This method facilitates the generation of 1,1‐disubstituted silacyclobutanes with a remarkable tolerance for various functional groups. This approach serves as a complementary and more step‐economical alternative to the commonly used yet moisture‐ and air‐sensitive nucleophilic substitution reactions involving Grignard or lithium reagents. Our initial mechanistic studies indicate that this reaction is initiated by oxidative cleavage of the Si−Cl bond in 1‐chlorosilacyclobutanes, which represents a distinct mechanism from the previously documented reductive coupling processes involving carbon electrophiles and chlorosilanes. Herein, a Ni‐catalyzed reductive protocol was developed for the synthesis of 1,1‐disubstituted silacyclobutanes, which are well‐known lynchpin intermediates in organosilicon synthesis. Unlike conventional methods, our protocol elegantly avoids the use of moisture‐ and air‐sensitive Grignard or lithium reagents, offering a markedly more step‐efficient and functionally tolerant approach. was developed.