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Cimpeanu V Parvulescu VI Amorós P Beltrán D Thompson JM Hardacre C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4640-4646
Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity. 相似文献
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Yong-Chul Jeong 《Tetrahedron letters》2004,45(50):9249-9252
Sterically hindered chiral Schiff base ligands 4a-d were prepared from an aldehyde derived from BINOL. The vanadium complexes of the ligands catalyze an efficient, enantioselective H2O2-promoted sulfoxidation of alkyl aryl sulfides, and enantioselectivities as high as 98-99% ee are observed in the sulfoxidation of benzyl aryl sulfides. 相似文献
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Enantioselective Sulfoxidation Catalyzed by a Bisguanidinium Diphosphatobisperoxotungstate Ion Pair
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Xinyi Ye Adhitya Mangala Putra Moeljadi Kek Foo Chin Prof. Dr. Hajime Hirao Dr. Lili Zong Prof. Dr. Choon‐Hong Tan 《Angewandte Chemie (International ed. in English)》2016,55(25):7101-7105
The first enantioselective tungstate‐catalyzed oxidation reaction is presented. High enantioselectivities were achieved for a variety of drug‐like phenyl and heterocyclic sulfides under mild conditions with H2O2, a cheap and environmentally friendly oxidant. Synthetic utility was demonstrated through the preparation of (S)‐Lansoprazole, a commercial proton‐pump inhibitor. The active ion‐pair catalyst was identified to be bisguanidinium diphosphatobisperoxotungstate using Raman spectroscopy and computational studies. 相似文献
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N-Alkyl-oxaziridines react in the presence of a nucleophile as an oxygenating agent; in the absence of a nucleophile, an isomerization reaction is observed. This study describes the synthesis of two new dihydroisoquinoline oxaziridines and their reactivity in an acid-promoted reaction in the presence and absence of sulfides. 相似文献
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Dramatic Influence of an Anionic Donor on the Oxygen‐Atom Transfer Reactivity of a MnV–Oxo Complex
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Heather M. Neu Dr. Matthew G. Quesne Tzuhsiung Yang Dr. Katharine A. Prokop‐Prigge Prof. Kyle M. Lancaster James Donohoe Prof. Serena DeBeer Dr. Sam P. de Visser Prof. David P. Goldberg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14584-14588
Addition of an anionic donor to an MnV(O) porphyrinoid complex causes a dramatic increase in 2‐electron oxygen‐atom‐transfer (OAT) chemistry. The 6‐coordinate [MnV(O)(TBP8Cz)(CN)]? was generated from addition of Bu4N+CN? to the 5‐coordinate MnV(O) precursor. The cyanide‐ligated complex was characterized for the first time by Mn K‐edge X‐ray absorption spectroscopy (XAS) and gives Mn?O=1.53 Å, Mn?CN=2.21 Å. In combination with computational studies these distances were shown to correlate with a singlet ground state. Reaction of the CN? complex with thioethers results in OAT to give the corresponding sulfoxide and a 2e?‐reduced MnIII(CN)? complex. Kinetic measurements reveal a dramatic rate enhancement for OAT of approximately 24 000‐fold versus the same reaction for the parent 5‐coordinate complex. An Eyring analysis gives ΔH≠=14 kcal mol?1, ΔS≠=?10 cal mol?1 K?1. Computational studies fully support the structures, spin states, and relative reactivity of the 5‐ and 6‐coordinate MnV(O) complexes. 相似文献
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A series of chiral Schiff bases ( L 1 – L 5 ) with different substituents in the salicylidenyl unit were prepared from condensation of 3‐aryl‐5‐ tert ‐butylsalicylaldehyde derivatives and optically active amino alcohols. Bromination of 3‐phenyl‐5‐ tert ‐butylsalicylaldehyde gave an unexpected product 3‐(4‐bromophenyl)‐5‐bromosalicylaldehyde, from which the corresponding Schiff base ligands L 6 and L 7 , derived from (S)‐valinol and (S)‐ tert ‐leucinol, respectively, were prepared. Ligands L 1 – L 7 were applied to the vanadium‐catalyzed asymmetric oxidation of aryl methyl sulfides. Under the optimal conditions, the oxidation of the thioanisole with H2O2 as oxidant in CH2Cl2 catalyzed by VO(acac)2‐ L 1 – L 7 gives good yields (74–83%) with moderate enantioselectivity (58–77% ee). Ligand L 7 , containing a 4‐bromophenyl group on the 3‐position and a Br atom on the 5‐position of the salicylidenyl moiety, displays an 80–90% ee for vanadium‐catalyzed oxidation of methyl 4‐bromophenyl sulfide and methyl 2‐naphthyl sulfide. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
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Gabriella Santoni Dr. Miriam Mba Dr. Marcella Bonchio Dr. William A. Nugent Cristiano Zonta Dr. Giulia Licini Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(2):645-654
The stereoselective oxidation of differently functionalised benzyl phenyl sulfides has been examined by using enantiopure TiIV trialkanolamine complexes. These complexes efficiently catalyse the sulfoxidation with good stereoselectivities. The data highlight the contribution to the stereoselectivity of steric effects and non‐covalent π–π interactions between the aromatic rings of the TiIV complex and those pertaining to the substrates. Enantiomeric excesses have been correlated with the electrostatic potential surfaces (EPS) of the reacting sulfides. The overall study leads to a mechanistic interpretation that explains the stereoselectivity of the system and dissects the role of aromatic and steric interactions in the stereoselective process. 相似文献