The Peterson olefination reaction is the silicon analog of the Wittig reaction.1 It offers significant advantage in terms of atom economy over the Wittig reaction and does not produce crystalline by-products. Despite these advantages the Peterson olefination remains under-utilized presumably due to the additional synthetic effort required to produce the required silylated anions. In this presentation a two step synthesis of arylmethylene bis-trimethylsilanes 1  (10 examples) using a twice repeated LiNK (BuLi/KOtBu/TMP(H)) metalation2 / TMSCl electrophile reaction sequence on substituted toluenes will be described. Reagents 1  are bench stable and can be viewed as silylated anion equivalents. The silyated anion can be generated from 1  under non-cryogenic conditions by either catalytic fluoride or trimethylsilonate and effectively participates in olefination of aldehydes and ketones. The nature of the bis-trimethylsilane activation, the mechanistic cycle and control of the stereochemical outcome will be discussed.1. Peterson, D.J. J. Org. Chem. 1968  , 33, 780.2. Fleming, P.; O'Shea, D.F. J. Am. Chem. Soc. 2011  , 133, 1698.

Bench stable reagents for Peterson olefination reactions

245th National Meeting (2013)

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