Acid-catalyzed reactions of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl)oxiran. A new synthesis of functional-group-substituted vinylsilanes

The magnesium bromide-diethyl etherate-catalyzed ring-opening of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl) oxiran 2 with thiophenols affords (1-trimethylsilylvinyl)sulfides 3 and the (1-bromovinyl) silane 4. Nucleophilic attack occurs regioselectively at the position alpha- to silicon. The compound 2 has been converted into the (1-trimethylsilylvinyl) amide 5 with an excess of acetonitrile and into the (1-trimethylsilylvinyl) acetate 6 with acetic acid/acetic anhydride. These reactions proceed with catalytic amounts of boron trifluoride-diethylether. Treatment of 2 with acetic acid alone gives naphthaldehyde. The epoxide 2 reacts also with MgBr(2)center dot OEt(2), MeLi/CuI, HX (X=Br or Cl) and LiAlH(4) with nucleophilic attack at the bis(trimethylsilyl)-substituted carbon. (C) 2011 Elsevier B.V. All rights reserved.