75186-45-7Relevant academic research and scientific papers
Cationic Chiral Fluorinated Oxazaborolidines. More Potent, Second-Generation Catalysts for Highly Enantioselective Cycloaddition Reactions
Mahender Reddy, Karla,Bhimireddy, Eswar,Thirupathi, Barla,Breitler, Simon,Yu, Shunming,Corey
supporting information, p. 2443 - 2453 (2016/03/08)
The coordination of chiral ligands to Lewis acid metal derivatives, a useful strategy for enantioselective, electrophilic catalysis, generally leads to a lower level of catalytic activity than that of the original uncomplexed compound. Activation by furth
Remote trimethylsilyl groups interfering with the ortho deprotonation of fluoroarenes and chloroarenes
Heiss, Christophe,Marzi, Elena,Mongin, Florence,Schlosser, Manfred
, p. 669 - 675 (2007/10/03)
(2-Fluorophenyl)trimethylsilane (2-F) and (2-chlorophenyl)-trimethylsilane (2-Cl) react with sec-butyllithium or lithium 2,2,6,6-tetramethylpiperidide under permutational hydrogen/metal interconversion (metalation) more slowly than, respectively, the corr
Fluorodesilylations of fluorophenyltrimethylsilanes with elemental fluorine: Discovery of a novel 1,2-migration of the trimethylsilyl group
Stuart, Alison M.,Coe, Paul L.,Moody, David J.
, p. 179 - 184 (2007/10/03)
The main product in the direct elemental fluorination of 4-fluorophenyltrimethylsilane was 1,4-difluorobenzene, produced by the ipso electrophilic substitution of the trimethylsilyl group. An unexpected product, 2,5-difluorophenyltrimethylsilane, was also formed as the result of a novel 1,2-migration of the trimethylsilyl group. The same trimethylsilyl 1,2-shifts were observed in the elemental fluorinations of 2-fluoro-and 2,4-difluoro-phenyltrimethylsilanes. We propose that the carbocations formed in the rearrangements were stabilised by the mescineric effect of the α-fluorine and the greater stability of these intermediates provided the driving force for the trimethylsilyl group migrations. Although the main products in all of the fluorinations were the fluorodesilylated product, the reactions were not totally regioselective and some competing fluorodeprotonation also occurred in the reactions of 2-fluoro-and 2,4-difluoro-phenyltrimethylsilanes. The role of protic acids and Lewis acids in particular triflic acid, trifluoroacetic acid and boron trifluoride in a variety of co-solvents, respectively, was crucial in all the fluorinations we studied, experiments done in their absence gave very poor yields. Optimal conditions for fluorination of silylated substrates are described.
