76274-76-5Relevant academic research and scientific papers
Photoredox Cross-Coupling: Ir/Ni Dual Catalysis for the Synthesis of Benzylic Ethers
Karakaya, Idris,Primer, David N.,Molander, Gary A.
supporting information, p. 3294 - 3297 (2015/07/15)
Single-electron transmetalation has emerged as an enabling paradigm for the cross-coupling of Csp3 hybridized organotrifluoroborates. Cross-coupling of α-alkoxymethyltrifluoroborates with aryl and heteroaryl bromides has been demonstrated by employing dual catalysis with a combination of an iridium photoredox catalyst and a Ni cross-coupling catalyst. The resulting method enables the alkoxymethylation of diverse (hetero)arenes under mild, room-temperature conditions. (Chemical Equation Presented).
Preparation of potassium alkoxymethyltrifluoroborates and their cross-coupling with aryl chlorides
Molander, Gary A.,Canturk, Belgin
supporting information; experimental part, p. 2135 - 2138 (2009/05/26)
(Chemical Equation Presented) A wide variety of alkoxymethyltrifluoroborate substrates were prepared via SN2 displacement of potassium bromomethyltrifluoroborate with various alkoxides in excellent yields. These alkoxymethyltrifluoroborates were effectively cross-coupled with several aryl chlorides. This method provides a unique dissonant disconnect that allows greater flexibility in the design of new and improved synthetic pathways.
A highly efficient method for the reductive etherification of carbonyl compounds with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride
Iwanami, Katsuyuki,Seo, Hana,Tobita, Yuki,Oriyama, Takeshi
, p. 183 - 186 (2007/10/03)
Facile reductive etherification of carbonyl compounds can be conveniently performed by reaction with triethylsilane and alkoxytrimethylsilane catalyzed by iron(III) chloride. The corresponding alkyl ethers, including benzyl and allyl ethers, of the reduced alcohols were obtained in good to excellent yields under mild reaction conditions.
Intramolecular Generation of Oxonium Ylides from Functionalized Arylcarbenes
Kirmse, Wolfgang,Kund, Klaus
, p. 1465 - 1473 (2007/10/02)
Arylcarbenes carrying alkoxyalkyl groups in the ortho position have been generated by flash pyrolysis and photolysis of appropriate tosylhydrazone sodium salts.In the gas phase and in a aprotic solvents, interaction of the carbenes with the lone electron pairs of oxygen competes efficiently with insertion into C-H bonds.Both five- and six-membered cyclic oxonium ylides have been generated.The ylides 23, 37, 61b, and 74 undergo 1,2 shifts of benzyl groups with ease, even if ring contraction to highly strained benzocyclobutenes is involved (23, 74).The oxonium ylides37 and 61b strongly prefer the nonconcerted Stevens rearrangement to the sigmatropic Sommelet rearrangement, in contrast to analogous ammonium ylides.Alkyl shifts occur to a very minor extent, if at all.Evidence is presented that alcohols intercept both the carbenes and the oxonium ylides.Protonation of the ylides leads to cyclic oxonium ions, which undergo nucleophilic cleavage of the C-O bonds.Acid catalyzed decomposition of the appropriate diazo compounds gives rise to six-membered, but not to five-membered, cyclic oxonium ions, thus confirming the different intramolecular reactivities of arylcarbenes and benzyl cations.The efficiency of carbene interception increases with increasing acidity of the medium, suggesting nucleophilic behavior (protonation) of the arylcarbenes.
