101-48-4Relevant articles and documents
Hypoiodous acid-catalyzed regioselective geminal addition of methanol to vinylarenes: synthesis of anti-Markovnikov methyl acetals
Peraka, Swamy,Mameda, Naresh,Marri, Mahender Reddy,Kodumuri, Srujana,Chevella, Durgaiah,Sripadi, Prabhakar,Nama, Narender
, p. 73732 - 73736 (2015)
A novel metal-free, catalytic geminal dimethoxylation of vinylarenes based on in situ generated HOI species from iodide salt and oxone is reported. The preliminary mechanistic investigations suggest that the key factor for achieving the anti-Markovnikov regioselectivity is the semipinacol rearrangement of an iodo functionalized intermediate, which is confirmed by an isotope labeling experiment. In addition, the reaction involves the de-iodination of a co-iodo intermediate via its oxidation to hypervalent iodine species rather than a common iodide abstraction by electrophiles. The HRESI-MS studies support the conversion of monovalent iodine containing intermediates to trivalent iodine intermediates during the catalytic conversion of aromatic alkenes into the corresponding terminal acetals.
Termolecular Trapping of Benzylchlorocarbene by Methanol
Liu, Michael T. H.,Subramanian, Ramasamy
, p. 1062 - 1064 (1984)
The trapping of benzylchlorocarbene by methanol is termolecular leading to a frequency factor of 2 x 105 l2 mol-2 s-1 and an activation energy of -4.5 kcal mol-1 (18.8 kJ mol-1).
Atom-economical synthesis of 3,3,3-trifluoropropanal dialkyl acetals through Pd/C catalyzed acetalization of 3,3,3-trifluoropropene
Kang, Jian-Ping,Lu, Ju-You,Li, Yang,Wang, Zhi-Xuan,Mao, Wei,Lu, Jian
, p. 39387 - 39391 (2016)
A facile and efficient procedure for one-step synthesis of 3,3,3-trifluoropropanal dialkyl acetals from readily available 3,3,3-trifluoropropene (TFP) has been developed. The catalyst can be recycled for 4 times without obvious deactivation. This process provides a novel and atom-economical synthetic strategy for the preparation of functional CF3-containing compounds.
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Uemura et al.
, p. 234 (1972)
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Palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups in scCO2
Jiang, Huan-Feng,Shen, Yan-Xia,Wang, Zhao-Yang
, p. 508 - 514 (2008)
Product control of palladium-catalyzed aerobic oxidation of terminal olefins with electron-withdrawing groups can be achieved through modifying reaction conditions. When the oxidant, such as CuCl2/O2, benzoquinone/O2 or O2, was present in scCO2, aerobic oxidation of terminal olefins goes smoothly. With enough MeOH and sufficient oxygen, acetalization preponderated over cyclotrimerization, while with little MeOH as co-solvent in scCO2 or no MeOH in DMF and an appropriate pressure of O2, cyclotrimerization of terminal olefins became the dominated reaction. When oxygen is absent and triethylamine was added into the reaction system, palladium-catalyzed C-N bond formation occurs to produce β-amino acid derivatives as the sole product.
Synthesis, structure and catalytic activity of a gold(i) complex containing 1,2-bis(diphenylphosphino)benzene monoxide
Hahn, Christine,Cruz, Leticia,Villalobos, Amanda,Garza, Liliana,Adeosun, Samuel
, p. 16300 - 16309 (2014)
The gold(i) complex [Au(dppbO)Cl] was synthesized by reaction of Na[AuCl4]·2H2O with 1,2-bis(diphenylphosphino)benzene (dppb) in the presence of water. This is a new method for the synthesis of a bisphosphine monoxide gold(i) complex. The new gold(i) complex was characterized by NMR spectroscopy and X-ray crystal structure analysis. In the solid state structure a relatively short contact between the oxygen atom of the phosphine oxide group and the gold center was observed. The catalytic activity of [Au(dppbO)Cl] was tested for three different intermolecular alkyne hydrofunctionalization reactions. Silver tetrafluoroborate was used as co-catalyst for halide abstraction. While the bisphosphine monoxide gold(i) complex showed moderate activity for the hydration of various alkynes and the hydroamination of phenyl acetylene, high activity was observed for the hydroarylation of ethylpropiolate. Electron-rich arenes add very fast to the C-C triple bond but with relatively low selectivity.
TRIMETHYLSILYLFLUOROSULFONATE (TMSOFs): AN ALTERNATIVE TO TMS TRIFLATE AS A SOURCE OF Me3Si+
Lipshutz, Bruce H.,Burgess-Henry, Jana,Roth, Gregory P.
, p. 995 - 998 (1993)
Generation of trimethylsilylfluorosulfonate in situ provides a useful source of TMS+, the reactivity of which is essentially equivalent to that of TMS triflate.Its precursors, in particular FSO3H, are less costly than those of TMSOTf or the reagent itself.
Substituent and Temperature Effects on the Reactions of Benzylchlorocarbene with Alcohol
Liu, Michael T. H.,Subramanian, Ramasamy
, p. 1233 - 1240 (1986)
The insertion reaction of the para-substituted benzylchlorocarbenes with methanol shows a second-order dependence in methanol, but only a first-order dependence in ethylene glycol.The results are consistent with a mechanism whereby the carbene inserts into the O-H bond of the alcohol dimer or oligomer by electrophilic attack of the carbene on the oxigenone pair to produce a reversibly formed ylide intermediate.The effects of the substituents indicate that electron-releasing group favours rearrangement while electron-withdrawing group facilitates insertion.Photolysis of halogenodiazirines in methanol at low temperatures give rise to V-shaped Arrhenius behaviour and the importance of N2 in influencing the reactivity of the singlet halogenocarbene in the matrix is demonstrated.
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Winstein,Ingraham
, p. 1738,1741 (1955)
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Electrochemical oxidative decarboxylation and 1,2-aryl migration towards the synthesis of 1,2-diaryl ethers
Bu, Faxiang,Hu, Xia,Lei, Aiwen,Lu, Lijun,Wang, Shengchun,Zhang, Heng
, p. 10000 - 10004 (2020/10/06)
Carboxylic acid compounds are important chemicals and are widely present in various natural products. They are not only nucleophiles, but also radical precursors. Classic transition-metal-catalyzed and photochemical decarboxylation have shown their excellent site selectivity in radical chemistry. However, electrochemical decarboxylation with a long history hasn't got enough attention in recent years. In this work, the electrochemical oxidative decarboxylation and 1,2-aryl migration of 3,3-diarylpropionic acids have been introduced to construct C-O bonds with alcohols. Remarkably, this transformation can proceed smoothly without metal catalysts and external oxidants.
Nickel-Catalyzed Chemoselective Acetalization of Aldehydes With Alcohols under Neutral Conditions
Subaramanian, Murugan,Landge, Vinod G.,Mondal, Akash,Gupta, Virendrakumar,Balaraman, Ekambaram
supporting information, p. 4557 - 4562 (2019/08/30)
A molecularly defined NiII-complex catalyzing the chemoselective acetalization of aldehydes with alcohols under neutral conditions is reported. The reaction is general, efficient and showed a wide substrate scope (including aliphatic aldehydes) as well as excellent functional group tolerance. Reusability of the present nickel catalyst is also demonstrated.
