Direct α‐Siladifluoromethylation of Lithium Enolates with Ruppert‐Prakash Reagent via CF Bond Activation

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<jats:title>Abstract</jats:title><jats:p>The direct α‐siladifluoromethylation of lithium enolates with the Ruppert–Prakash reagent (CF<jats:sub>3</jats:sub>TMS) is shown to construct the tertiary and quaternary carbon centers. The Ruppert–Prakash reagent, which is versatile for various trifluoromethylation as a trifluoromethyl anion (CF<jats:sub>3</jats:sub><jats:sup>−</jats:sup>) equivalent, can be employed as a siladifluoromethyl cation (TMSCF<jats:sub>2</jats:sub><jats:sup>+</jats:sup>) equivalent by CF bond activation due to the strong interaction between lithium and fluorine atoms.</jats:p>

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