In amongst the considerable chemistry of acetylenes there lies some unique chemistry of alkynylsilanes (silylacetylenes) some of which is reviewed herein. This unique character is exemplified not only in the silyl protection of the terminal C–H of acetylenes, but also in the ability of the silyl group to be converted into other functionalities after reaction of the alkynylsilane and to its ability to dictate and improve the regioselectivity of reactions at the triple bond. This, when combined with the possible subsequent transformations of the silyl group, makes their chemistry highly versatile and useful.1 Introduction2 Safety3 Synthesis4 Protiodesilylation5 Sonogashira Reactions6 Cross-Coupling with the C–Si Bond7 Stille Cross-Coupling8 Reactions at the Terminal Carbon9 Cross-Coupling with Silylethynylmagnesium Bromides10 Reactions of Haloethynylsilanes11 Cycloaddition Reactions11.1 Formation of Aromatic Rings11.2 Diels–Alder Cyclizations11.3 Formation of Heterocycles11.4 Formation of 1,2,3-Triazines11.5 [2+3] Cycloadditions11.6 Other Cycloadditions12 Additions to the C≡C Bond13 Reactions at the C–Si Bond14 Miscellaneous Reactions
Enantio‐ and Regioconvergent Nickel‐Catalyzed C(sp3)–C(sp3) Cross‐Coupling of Allylic Electrophiles Steered by a Silyl Group
