Direct α-siladifluoromethylation of lithium enolates with Ruppert-Prakash reagent via C-F bond activation

Ryota Hashimoto; Toshiaki Iida; Kohsuke Aikawa; Shigekazu Ito; Koichi Mikami

doi:10.1002/chem.201304473

Direct α-siladifluoromethylation of lithium enolates with Ruppert-Prakash reagent via C-F bond activation

Chemistry. 2014 Mar 3;20(10):2750-4. doi: 10.1002/chem.201304473. Epub 2014 Feb 7.

Authors

Ryota Hashimoto¹, Toshiaki Iida, Kohsuke Aikawa, Shigekazu Ito, Koichi Mikami

Affiliation

¹ Department of Applied Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8552 (Japan).

PMID: 24590495
DOI: 10.1002/chem.201304473

Abstract

The direct α-siladifluoromethylation of lithium enolates with the Ruppert-Prakash reagent (CF3 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 (CF3 (-) ) equivalent, can be employed as a siladifluoromethyl cation (TMSCF2 (+) ) equivalent by CF bond activation due to the strong interaction between lithium and fluorine atoms.

Keywords: CF activation; Ruppert-Prakash reagent; difluoromethylation; lithium enolate; umpolung.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Fluorine / chemistry*
Hydrocarbons, Fluorinated / chemistry*
Indicators and Reagents / chemistry*
Lithium / chemistry*
Methylation
Molecular Structure
Onium Compounds / chemistry*

Substances

Hydrocarbons, Fluorinated
Indicators and Reagents
Onium Compounds
Fluorine
Lithium