Abstract
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
Key words
alkynes - azides - cross-coupling - enynes - protecting groups - silicon - Stille
reaction
