84413-74-1Relevant academic research and scientific papers
A study of enantioselective syntheses by Sharpless asymmetric oxidation for aryl sulfoxides containing oxygen groups at the ortho position
Takei, Takanori,Takayama, Jun,Xuan, Meiyan,Tomoda, Misa,Miyamae, Hiroshi,Sakamoto, Takeshi
, (2021/03/16)
Abstract: While ortho-alkoxy aryl sulfoxides including various substituents were synthesized by Sharpless asymmetric oxidation reaction, we optimized the reaction conditions and screened better combination of starting materials to obtain high enantioselectivity. The result suggested new information that electron-withdrawing substituents on the aromatic ring have a strong influence upon enantioselectivity of the products. Also, several chiral ligands for Sharpless asymmetric oxidation reaction were evaluated to improve the enantioselectivity. Graphic abstract: High enantioselectivity of ortho-alkoxy aryl chiral sulfoxides have been achieved by Sharpless oxidation reaction using Ti(O-i-Pr)4 and diethyl tartrate under anhydrous condition. In particular, the enantioselctivity of products was influenced by electron-withdrawing substituents on the aromatic ring, such as nitro, ester and aldehyde groups.[Figure not available: see fulltext.]
Ionic liquid-functionalized amphiphilic Janus nanosheets afford highly accessible interface for asymmetric catalysis in water
Li, Chaoping,Liu, Su,Pi, Yibing,Feng, Jingwen,Liu, Zewei,Li, Shiye,Tan, Rong
, p. 236 - 245 (2021/02/16)
High oil/water interfacial area together with accessible interfaces for regents is the key to achieving efficient asymmetric catalysis in water. Herein, by taking advantage of the excellent interfacial activity of Janus nanosheets (JNS), as well as the unique compatibility of imidazolium ionic liquid (IL), we developed a series of IL-functionalized amphiphilic Janus mesosilica nanosheets which afford highly accessible reaction interfaces for highly enantioselective sulfoxidation in water. The JNS-typed chiral salen TiIV catalysts were prepared by selectively decorating hydrophobic chiral salen TiIV complex on one side of Janus mesosilica nanosheets through the imidazolium-based IL linker. Benefiting from the two-dimensional porous Janus structure, as well as the compatible IL linker, the IL-tagged JNS catalysts afforded high oil/water interfacial areas and highly accessible reaction interface for sulfides and H2O2, significantly accelerating asymmetric sulfoxidation in water using H2O2 as an oxidant. In addition, they can be facilely recovered for stable reuse by simple centrifugation.
Two enantiocomplementary Baeyer-Villiger monooxygenases newly identified for asymmetric oxyfunctionalization of thioether
Liu, Yafei,Ni, Ye,Wei, Shiyu,Xu, Guochao,Zhou, Jieyu
, (2021/08/19)
Two enantiocomplementary Baeyer-Villiger monooxygenases RaBVMO and AmBVMO were identified by genome mining for the asymmetric sulfoxidation. Both recombinant BVMOs have optimal pH of 9.0 and temperature of 35 °C. The half-lives of RaBVMO and AmBVMO at 30 °C were 24.4 and 24.6 h. RaBVMO and AmBVMO exhibited broad substrate spectrum and could catalyze the oxidization of various compounds including fatty ketones, cyclic ketones, and thioethers. Kinetic parameters analysis revealed that both RaBVMO and AmBVMO displayed higher catalytic efficiency toward thioanisole than cyclohexanone. As much as 50 mM thioanisole could be completely oxidized by AmBVMO and RaBVMO with 99% (R) and 95% (S), respectively. Molecular docking analysis further provides evidence for the complementary enantioselectivity of RaBVMO and AmBVMO. Our results demonstrate the potential application of the two novel BVMOs in asymmetric synthesis of sulfoxides.
Chiral Analogues of PFI-1 as BET Inhibitors and Their Functional Role in Myeloid Malignancies
Altenburg, Bianca,Frings, Marcus,Sch?bel, Jan-Hendrik,Go?en, Jonas,Pannen, Kristina,Vanderliek, Kim,Rossetti, Giulia,Koschmieder, Steffen,Chatain, Nicolas,Bolm, Carsten
supporting information, p. 1928 - 1934 (2020/11/09)
Structural analogues of PFI-1 varying at the sulfur core were prepared, and their activities as BET inhibitors in myeloid cell lines and primary cells from patients with acute myeloid leukemia were studied. Docking calculations followed by molecular dynam
Light-controlled cooperative catalysis of asymmetric sulfoxidation based on azobenzene-bridged chiral salen TiIVcatalysts
Fu, Wenqin,Gao, Mengqiao,Li, Chaoping,Pi, Yibing,Tan, Rong,Wang, Weiying,Yin, Donghong
supporting information, p. 5993 - 5996 (2020/06/04)
Incorporation of azobenzene into the linker of bimetallic chiral salen TiIVcatalysts allowed the photoswitchable arrangement of the two Ti(salen) units throughcis/transphotoisomerization of azobenzene. The differently arranged Ti(salen) units changed their cooperative function to reflect the positional relationships, as a result, their efficiency as cooperative catalysts in asymmetric sulfoxidation could be readily controlled by light stimuli.
An ionic liquid-functionalized amphiphilic Janus material as a Pickering interfacial catalyst for asymmetric sulfoxidation in water
Zhang, Mingjie,Tang, Zhiyang,Fu, Wenqin,Wang, Weiying,Tan, Rong,Yin, Donghong
supporting information, p. 592 - 595 (2019/02/05)
Ionic liquid-functionalized amphiphilic Janus chiral salen TiIV catalysts were prepared by partial hydrophobic modification of silica with a chiral salen TiIV complex through an imidazolium ionic liquid (IL) linker. By optimizing their hydrophobic/hydrophilic balance, the IL-functionalized JNP materials exhibited excellent interfacial activity, significantly accelerating asymmetric sulfoxidation in water through the formation of stable Pickering emulsions. Moreover, catalyst recovery was readily achieved using centrifugation.
Titanium(iv)-folded single-chain polymeric nanoparticles as artificial metalloenzyme for asymmetric sulfoxidation in water
Zhang, Yaoyao,Wang, Weiying,Fu, Wenqin,Zhang, Mingjie,Tang, Zhiyang,Tan, Rong,Yin, Donghong
supporting information, p. 9430 - 9433 (2018/08/28)
Intrachain TiIV-oxazoline complexation together with hydrophobic interaction triggered the self-folding of an oxazoline-containing single polymeric chain in water. The formed TiIV-folded single-chain polymeric nanoparticles (SCPNs) acted as metalloenzyme-mimetic catalysts in asymmetric sulfoxidation in water owing to their organized, compartmentalized structure, effective site isolation, and also secondary coordination sphere provided by a copolymer backbone. In addition, they also could be facilely recovered for reuse by simple thermo-controlled separation.
Enantioselective Aromatic Sulfide Oxidation and Tandem Kinetic Resolution Using Aqueous H2O2 and Chiral Iron–Bis(oxazolinyl)bipyridine Catalysts
Jalba, Angela,Régnier, Noémie,Ollevier, Thierry
, p. 1628 - 1637 (2017/04/06)
An efficient method for the oxidation of aromatic sulfides has been developed by using aqueous H2O2, catalyzed by the in situ generated chiral Fe/6,6′-bis(4-isopropyloxazolin-2-yl)-2,2′-bipyridine (bipybox-iPr) complex. The corresponding sulfoxides were obtained with high enantioselectivities (up to 98.5:1.5 er) and in good yields (up to 61 %) when the mono-oxidation of the sulfides was performed in combination with the kinetic resolution of the sulfoxide into the sulfone.
Bio-inspired single-chain polymeric nanoparticles containing a chiral salen TiIV complex for highly enantioselective sulfoxidation in water
Zhang, Yaoyao,Tan, Rong,Gao, Mengqiao,Hao, Pengbo,Yin, Donghong
, p. 1182 - 1193 (2017/08/14)
A series of bio-inspired single-chain polymeric nanoparticles (SCPNs) containing a chiral salen TiIV complex in their hydrophobic cavity were constructed from the synthesized amphiphilic copolymers of poly(NIPAAm-co-IL/Ti(salen)) (NIPAAm, N-isopropylacrylamide; IL/Ti(salen), vinylimidazolium ionic liquid-modified chiral salen TiIV complex). These SCPNs behaved as enzyme-mimetic catalysts due to compartmentalization and site isolation, mediating enantioselective oxidation of various sulfides in water with excellent yields (90-99%) and enantioselectivities (ee, 88-99%). In particular, the ee values observed for electron-rich substrates (>95% ee) represented the best results so far in titanium-salen systems. Moreover, the catalysts could be easily recovered for steady reuse by thermo-controlled separation due to thermo-responsive properties. This work first constructed titanium-containing biomimetic SCNPs for biocatalysis of enantioselective sulfoxidation in water.
Ultraviolet-responsive self-assembled metallomicelles for photocontrollable catalysis of asymmetric sulfoxidation in water
Gao, Mengqiao,Tan, Rong,Hao, Pengbo,Zhang, Yaoyao,Deng, Jiang,Yin, Donghong
, p. 54570 - 54580 (2017/12/12)
Self-assembled metallomicelles with ultraviolet (UV)-controlled morphologies were constructed from a synthesized azobenzene-containing amphiphilic chiral salen TiIV catalyst. The morphologies of the metallomicelles could be well adjusted by changing the UV irradiation time, and this was confirmed by TEM analyses. The UV-induced change in morphology potentially adjusted the catalyst concentration and/or accessibility in real-time, allowing photocontrollable catalysis of asymmetric sulfoxidation in water. UV-responsive catalytic activities with excellent selectivities were observed over the metallomicelles for a wide range of alkyl aryl sulfides. Moreover, a thermo-responsive NIPAAm block in the catalyst enables it to be easily recovered for steady reuse by thermo-controlled separation. This work constructed a photo-responsive metallomicellar system to carry out metallomicellar catalysis in a controllable way.
