Some Aspects of the Chemistry of Alkynylsilanes

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 Introduction 2 Safety 3 Synthesis 4 Protiodesilylation 5 Sonogashira Reactions 6 Cross-Coupling with the C–Si Bond 7 Stille Cross-Coupling 8 Reactions at the Terminal Carbon 9 Cross-Coupling with Silylethynylmagnesium Bromides 10 Reactions of Haloethynylsilanes 11 Cycloaddition Reactions 11.1 Formation of Aromatic Rings 11.2 Diels–Alder Cyclizations 11.3 Formation of Heterocycles 11.4 Formation of 1,2,3-Triazines 11.5 [2+3] Cycloadditions 11.6 Other Cycloadditions 12 Additions to the C≡C Bond 13 Reactions at the C–Si Bond 14 Miscellaneous Reactions