+ Site Statistics
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3 SiCF2 H



Bis(difluoromethyl)trimethylsilicate Anion: A Key Intermediate in Nucleophilic Difluoromethylation of Enolizable Ketones with Me3 SiCF2 H



Angewandte Chemie 55(41): 12632



A pentacoordinate bis(difluoromethyl)silicate anion, [Me3 Si(CF2 H)2 ](-) , is observed for the first time by the activation of Me3 SiCF2 H with a nucleophilic alkali-metal salt and 18-crown-6. Further study on its reactivity by tuning the countercation effect led to the discovery and development of an efficient, catalytic nucleophilic difluoromethylation of enolizable ketones with Me3 SiCF2 H by using a combination of CsF and 18-crown-6 as the initiation system. Mechanistic investigations demonstrate that [(18-crown-6)Cs](+) [Me3 Si(CF2 H)2 ](-) is a key intermediate in this catalytic reaction.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 057311051

Download citation: RISBibTeXText

PMID: 27552967

DOI: 10.1002/anie.201605280


Related references

Nucleophilic difluoromethylation of primary alkyl halides using difluoromethyl phenyl sulfone as a difluoromethyl anion equivalent. Organic Letters 6(23): 4315-4317, 2004

Tuning the reactivity of difluoromethyl sulfoximines from electrophilic to nucleophilic: stereoselective nucleophilic difluoromethylation of aryl ketones. Journal of the American Chemical Society 134(41): 16999-17002, 2012

Gem-Difluoroolefination of diaryl ketones and enolizable aldehydes with difluoromethyl 2-pyridyl sulfone: new insights into the Julia-Kocienski reaction. Chemistry 20(25): 7803-7810, 2014

Nucleophilic difluoromethylation and difluoromethylenation of aldehydes and ketones using diethyl difluoromethylphosphonate. Tetrahedron 64(49): 10977-10985, 2008

Radical Difluoromethylation of Thiols with (Difluoromethyl)triphenylphosphonium Bromide. Organic Letters 19(15): 4150-4153, 2017

N-Tosyl-S-difluoromethyl-S-phenylsulfoximine: a new difluoromethylation reagent for S-, N-, and C-nucleophiles. Organic Letters 11(10): 2109-2112, 2009

A Convenient Access to α-Mesyloxy Ketones from Enolizable Ketones Using Thallium(III) Methanesulphonate. Synlett 1992(05): 393-394, 1992

Iron-Catalyzed Difluoromethylation of Arylzincs with Difluoromethyl 2-Pyridyl Sulfone. Journal of the American Chemical Society 140(3): 880-883, 2018

A new method for the synthesis of difluoromethyl enol ethers by O-difluoromethylation of 1,3-diones with ClCF2CO2Et. Organic and Biomolecular Chemistry 13(11): 3432-3437, 2015

Copper-Catalyzed Difluoromethylation of Aryl Iodides with (Difluoromethyl)zinc Reagent. Organic Letters 18(15): 3686-3689, 2016

OnePot Synthesis of aFormyloxy Ketones from Enolizable Ketones. Synthetic Communications 38(3): 338-345, 2008

Copper-mediated aerobic (phenylsulfonyl)difluoromethylation of arylboronic acids with difluoromethyl phenyl sulfone. Chemical Communications 52(18): 3657-3660, 2016

S-((phenylsulfonyl)difluoromethyl)thiophenium salts: carbon-selective electrophilic difluoromethylation of β-ketoesters, β-diketones, and dicyanoalkylidenes. Angewandte Chemie 53(7): 1827-1831, 2014

Copper-mediated difluoromethylation of (hetero)aryl iodides and β-styryl halides with tributyl(difluoromethyl)stannane. Angewandte Chemie 51(48): 12090, 2012

Conversion of Methyl Ketones and Methyl Sulfones into α-Deutero-α,α-Difluoromethyl Ketones and α-Deutero-α,α-Difluoromethyl Sulfones in Three Synthetic Steps. Tetrahedron Letters 58(5): 396-400, 2017