Transition-Metal-Catalyzed Synthesis of α-Chiral Allylsilanes

Abstract

AbstractOver the past 30 years, the synthesis of α-chiral allylsilanes have attracted much interest. These compounds are indeed versatile building blocks and linchpins ranking among the most useful organic scaffolds due to the large number of transformations that both their C–Si bond and C–C double bond can undergo. They therefore occupy a unique place in the arsenal of the organic chemist, particularly for the synthesis of complex molecules. In this review, an overview of transition-metal-catalyzed syntheses of α-chiral allylsilanes is presented.1 Introduction2 Addition of Silylmetals2.1 Silylation of Allylic Electrophiles2.2 Conjugate Addition2.3 1,2-Addition to N-tert-Butylsulfonyl Imines2.4 Silaboration3 Addition of Nucleophiles3.1 Substitution of γ-Silylated Allylic Electrophiles3.2 1,4-Conjugate Addition to β-Silyl Enones and Enoates3.3 Reduction of γ-Silylated Allylic Carbonates4 Hydrosilylation4.1 1,4-Hydrosilylation of 1,3-Dienes4.2 1,2-Hydrosilylation of 1,3-Dienes4.3 1,2-Hydrosilylation of Allenes5 Cross-Coupling Reactions5.1 Cross-Coupling of Vinyl Halides5.2 Retroallylation of δ-Silylated Homoallylic Alcohols5.3 Multicomponent Cross-Coupling of 1,3-Dienes6 Insertion Reactions6.1 Vinylcarbenoid Insertion into Si–H Bonds6.2 Silylene Insertion into Allylic C–O Bonds7 Rearrangements7.1 Intramolecular γ-Silylation of Allylic Disilanyl Ethers7.2 Domino Isomerization–Claisen Rearrangement of γ-Silylated Bis(allylic) Ethers8 Miscellaneous9 Conclusion