On the radical brook rearrangement. Reactivity of alpha-silyl alcohols, alpha-silyl alcohol nitrite esters, and beta-haloacylsilanes under radical-forming conditions

J Org Chem. 2000 Apr 21;65(8):2292-304. doi: 10.1021/jo9912855.

Abstract

Two alkoxyl radical generation methods, lead tetraacetate treatment of alcohols and photolysis of nitrites, were applied to alpha-silyl alcohols 21 and to the corresponding nitrites 25 with a view to forming alpha-silyl alkoxyl radicals 23 and studying their possible radical Brook rearrangement to alpha-silyloxy carbon radicals 24. LTA treatment of 21 led to their quick and efficient conversion into mixed acetyl-silyl acetals 33 under very mild conditions. Photolysis of alpha-alkylmonosubstituted alpha-silyl nitrites 25 to the corresponding aldehydes is considered to proceed through alpha-silyl alkoxyl radical intermediates 23. A concerted process is, however, proposed for the case of the benzyl nitrites analogues. On the basis of these results, it is postulated that resonance stabilization can have a major influence on the evolution of alpha-silyl alkoxyl radicals: should this stabilization be possible, they quickly evolve by alpha-silyl fragmentation; otherwise, they tend to undergo radical Brook rearrangement. It was also found that the radical Brook rearrangement of alpha-silyl cyclopropyloxyl radicals generated from beta-bromoacylsilanes under standard tin-radical conditions is too slow to compete with beta-fragmentation.