Reactions of Silenes Additions to the Double Bond

As silenes represent a much more reactive higher energy it system than alkenes, it is not surprising that they show many of the reactions of alkenes as well as some behavior not generally exhibited by alkenes. However, the relative instability of silenes has meant that in most cases little mechanistic information on the observed reactions is available, and it is by no means certain in all cases that the same mechanism prevails for reactions of silenes and alkenes with the same reagent. 

Two reactions have come to be extensively used with silenes, arising from the need to trap the short-lived species cleanly and in high yield, as evidence either of their formation or of the extent of their formation. These are the addition of alcohols, usually methanol, across the double bond to yield an alkoxysilane, and the Diels-Alder reaction with a diene, often 2,3-dimethylbutadiene. Each is an example of the two different types of addition to the Si=C double bond. 

The stereochemistry of alcohol (and related reagents) addition to a silene is not known with certainty. The present authors have recently synthesized stable silenes where two geoisomers are possible (200) (also see Section VII). While NMR (1H, I3C, 29Si) data indicated the presence 

Thus it is clear that a wide variety of polar tr-bonded reagents will react with the silicon-carbon double bond. In general, the reactions can be explained on the basis of a two-step addition reaction initiated by nucleophilic attack on silicon. 

A second category of silene reactions involves interactions with tt-bonded reagents which may include homonuclear species such as 1,3-dienes, alkynes, alkenes, and azo compounds as well as heteronuclear reagents such as carbonyl compounds, imines, and nitriles. Four modes of reaction have been observed nominal [2 + 2] cycloaddition (thermally forbidden on the basis of orbital symmetry considerations), [2 + 4] cycloadditions accompanied in some cases by the products of apparent ene reactions (both thermally allowed), and some cases of (allowed) 1,3-dipolar cycloadditions. 

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