5558-08-7Relevant articles and documents
Iron-catalyzed π-activated C-O ether bond cleavage with C-C and C-H bond formation
Fan, Xiaohui,Cui, Xiao-Meng,Guan, Yong-Hong,Fu, Lin-An,Lv, Hao,Guo, Kun,Zhu, Hong-Bo
supporting information, p. 498 - 501 (2014/02/14)
A novel and efficient allylic alkylation reaction between π-activated ethers and allylsilane was realized under mild conditions through iron(III)-catalyzed C sp 3-O ether bond cleavage. The present protocol provides an attractive approach for the construction of sp3-sp3 C-C bonds and can be potentially applied for the selective reduction of benzyl and allyl ethers to their corresponding hydrocarbon compounds by using triethylsilane as a hydride-transfer reagent. A mild, economical, and environmentally friendly method for the construction of C sp 3-C sp 3 bonds through iron-catalyzed π-activated C-O ether bond cleavage is developed. In addition, this catalytic system can be used for the selective reduction of benzylic and allylic C-O ether bonds to C-H bonds. Copyright
Iron-Catalyzed π-Activated C-O Ether Bond Cleavage with C-C and C-H Bond Formation
Fan, Xiaohui,Cui, Xiao-Meng,Guan, Yong-Hong,Fu, Lin-An,Lv, Hao,Guo, Kun,Zhu, Hong-Bo
supporting information, p. 498 - 501 (2015/10/05)
A novel and efficient allylic alkylation reaction between π-activated ethers and allylsilane was realized under mild conditions through iron(III)-catalyzed C sp 3-O ether bond cleavage. The present protocol provides an attractive approach for the construction of sp3-sp3 C-C bonds and can be potentially applied for the selective reduction of benzyl and allyl ethers to their corresponding hydrocarbon compounds by using triethylsilane as a hydride-transfer reagent.
Iron-catalyzed N-alkylation using π-activated ethers as electrophiles
Fan, Xiaohui,Fu, Lin-An,Li, Na,Lv, Hao,Cui, Xiao-Meng,Qi, Yuan
supporting information, p. 2147 - 2153 (2013/04/10)
A new method for the synthesis of diverse N-alkylation compounds was developed via an iron-catalyzed etheric Csp3-O cleavage with the C-N bond formation in the reaction of π-activated ethers with various nitrogen-based nucleophiles. In addition, the mechanism of this reaction was investigated. The Royal Society of Chemistry 2013.
Laser flash photolysis study of arylcyclopropylcarbenium ions: Cation stabilizing abilities of cyclopropyl and phenyl groups
Kirmse, Wolfgang,Krzossa, Birgit,Steenken, Steen
, p. 7473 - 7477 (2007/10/03)
Arylcyclopropylcarbenium ions, Ar(c-Pr)CH+, were generated as transient intermediates by laser flash photolysis (LFP) of trans-2,3-diphenylaziridinimines of aryl cyclopropyl ketones in 2,2,2-trifluoroethanol (TFE). The carbocations are thought to arise by way of diazo compounds and carbenes. Rate constants for the unimolecular decay in TFE and for the bimolecular reaction with methanol in TFE were obtained for Ar(c-Pr)CH+ and for analogous arylphenylcarbenium ions, ArPhCH+. Within these series, the cation stabilizing abilities of cyclopropyl and phenyl groups are found to be similar in magnitude. However, cyclopropyl responds more strongly than phenyl to increasing electron demand. Hence cyclopropyl is superior to phenyl in cation stabilizing ability for Ar = Ph but inferior to phenyl for Ar = 4-MeOC6H4.
1,2-Hydrogen migration and alkene formation in the photoexcited states of alkylphenyldiazomethanes
?elebi, Sol,Leyva, Soccoro,Modarelli, David A.,Platz, Matthew S.
, p. 8613 - 8620 (2007/10/02)
Laser flash photolysis of alkylphenyldiazomethanes in the presence of pyridine produces easily detected ylides. The data indicate that photolysis of alkylphenyldiazomethanes leads to both carbene formation and direct formation of rearrangement products which do not derive from relaxed carbene intermediates.
Photolysis of 1,1,1-Triarylalkane. A New Photochemical Carbene Generation Process
Shi, Min,Okamoto, Yoshiki,Takamuku, Setsuo
, p. 3821 - 3824 (2007/10/02)
Upon UV irradiation in methanol some 1,1,1-triarylalkanes underwent an α,α-elimination of two aryl groups to give biaryls and the corresponding carbene intermediates, which inserted into the OH bond of the methanol to afford methyl ethers and/or underwent a 1,2-H shift to afford olefins.Furthermore, the efficieny of this elimination was highly dependent upon the bulkiness of the alkyl groups.
Photolysis of 1,1,1-triphenylalkanes
Shi,Okamoto,Takamuku
, p. 6709 - 6712 (2007/10/02)
Photolysis of 1,1,1-triphenylalkane in methanol gave biphenyl, 1-methoxy-1-phenylalkane, and 1-phenylalkene. The generation of the carbene intermediate by photo α,α-elimination of two phenyl groups was presumed.
CYCLOPROPYLCARBINYL COMPOUNDS FROM HOMOALLYLIC IODIDES
Previtera, Lucio,Monaco, Pietro,Mangoni, Lorenzo
, p. 1293 - 1294 (2007/10/02)
A simple synthesis of cyclopropylcarbinyl compounds based on the reaction of homoallylic iodides with silver salts in anhydrous medium is described.
Photochemistry of Arylbutadienes. Part 2. Preparation and Photochemistry of 1-(Substituted-aryl)butadienes. A Ground-state Substituent Effect on an Excited-state Reaction
Baldry, Peter J.
, p. 805 - 808 (2007/10/02)
Yields and quantum yields are reported for the photoaddition of methanol to 1-phenylbutadiene and eight substituted 1-phenylbutadienes.For allyl and homoallyl products log Φ correlates more satisfactorily with ground-state substituent constants than with excited-state constants; for cyclopropylmethyl products, no correlation is observed with either set of constants.
Photochemistry of Arylbutadienes. Part 3. Mechanisms of Photoaddition of Methanol to 1-Arylbutadienes
Baldry, Peter
, p. 809 - 815 (2007/10/02)
The mechanism of formation of methyl ethers from irradiation of 1-arylbutadienes in methanol has been studied by deuterium labelling, fluorescence quenching, sensitisation, and kinetic studies.Cyclopropylmethyl ethers arise by a bicyclobutane mechanism; allyl and homoallyl ethers are formed by reaction of methanol with the 1Bu-like excited singlet diene to produce carbocation intermediates.
