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