Jusong Yang, School of Chemistry and Materials, Yangzhou University, Yangzhou 225002, Jiangsu, China. E-mail: yangjusong@yzu.edu.cn
Abstract
Chiral organosilicon compounds are widely applied in frontier fields including synthetic chemistry, materials science, and pharmaceutical research. Thus, the design of green, operationally simple, and chemoselective strategies for the assembly of structurally sophisticated organosilicon frameworks is of paramount significance and continues to attract considerable attention. Silacyclobutanes (SCBs), a class of small-ring compounds with unique structural features, exhibit excellent reactivity due to their inherent ring strain. During the past decade, the transition-metal-catalyzed (Rh, Pd, Ni) regio- and enantioselective C–Si bond cleavage of silacyclobutanes has emerged as a powerful and complementary synthetic tool for accessing structurally diverse, functionalized chiral organosilanes. This review systematically surveys recent advances in transition-metal-catalyzed asymmetric cleavage of C–Si bonds in silacyclobutanes with various coupling partners, such as alkenes, alkynes, allenes, and carbonyls, for the construction of chiral functionalized organosilanes featuring carbon-centered, silicon-centered, or axially chiral stereogenic units. We also briefly discuss the associated reaction mechanisms, strategic modulation of reactivity and enantioselectivity, and prospective developments.
Keywords
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