84413-73-0Relevant 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.]
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
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.
Cooperative chiral salen TiIV catalyst supported on ionic liquid-functionalized graphene oxide accelerates asymmetric sulfoxidation in water
Xing, Chen,Deng, Jiang,Tan, Rong,Gao, Mengqiao,Hao, Pengbo,Yin, Donghong,Yin, Dulin
, p. 5944 - 5952 (2017/12/26)
A cooperative chiral salen TiIV catalyst was prepared by covalently appending multiple chiral salen TiIV complexes on a graphene oxide (GO) surface through a flexible ionic liquid (IL) linker. Characterization results confirmed the decoration of intact Ti(salen) units on the edges and planes of exfoliated GO with the imidazolium-IL spacer. The IL-functionalized GO nanosheets endowed the chiral salen TiIV catalyst with high water-dispersion, diminished diffusion limitation, and particularly a reinforced intramolecular cooperative effect. The cooperative catalyst was thus highly efficient and universally applicable in the catalysis of asymmetric sulfoxidation in water, affording high yields of various chiral sulfoxides with excellent enantioselectivities, while traditional chiral salen TiIV complex was far less active. More importantly, the heterogeneous catalyst was perfectly stable and could be reused several times without significant loss of activity and selectivity.
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.
Cooperative chiral salen TiIV catalysts with built-in phase-transfer capability accelerate asymmetric sulfoxidation in water
Zhao, Guangwu,Tan, Rong,Zhang, Yaoyao,Luo, Xuanfeng,Xing, Chen,Yin, Donghong
, p. 24704 - 24711 (2016/03/15)
A series of cooperative chiral salen TiIV catalysts with inherent phase-transfer capability were prepared by covalently bridging double chiral salen TiIV units with various polyethylene glycol (PEG)-based dicationic ionic liquid (IL) linkers. Characterization results suggested the presence of polyether-based IL spacers and intact active sites in the catalysts. The polyether-based dicationic IL spacer not only enforced an intramolecular, cooperative reaction pathway favored for the asymmetric suloxidation, but also endowed the bimetallic catalysts with built-in phase transfer capability. High yields of chiral sulfoxides (in the range of 74-90%) with excellent ee values (in the range of 85-91%) were achieved within 45 min when the asymmetric oxidation of methyl phenyl sulfide, methyl p-methoxyphenyl sulfide, and methyl o-methoxyphenyl sulfide were performed in water. The catalytic efficiency was significantly higher than that over neat complex (yields, 10-16% and ee values, 77-79%). More attractively, the phase transfer catalysts could be facilely recovered by solvent precipitation for efficient reuse.
Thermo-responsive self-assembled metallomicelles accelerate asymmetric sulfoxidation in water
Zhang, Yaoyao,Tan, Rong,Zhao, Guangwu,Luo, Xuanfeng,Xing, Chen,Yin, Donghong
, p. 62 - 71 (2016/01/25)
A series of novel chiral salen TiIV catalysts with thermo-responsive surfactant properties were prepared by covalently appending a chiral salen TiIV complex on the hydrophobic block of thermo-responsive amphiphilic copolymers of poly(N-isopropylacrylamide-co-N,N-dimethyl acrylamide) (poly (NIPAAM-co-DMAAM)). Characterization results suggested self-assembly behavior of the catalysts in water at room temperature. The self-assembled metallomicelles induced a micellar catalytic approach in asymmetric sulfoxidation in water using H2O2 as an oxidant, leading to significant rate acceleration and remarkable high selectivity. Quantitative conversion (>99%) of methyl phenyl sulfide with up to 96% chemoselectivity and 95% enantioselectivity was achieved over 0.5 mol% of PN70D7-C even within 30 min, whereas neat complex was far less efficient (9% conversion with 72% chemoselectivity and 79% enantioselectivity). Moreover, the catalysts could be easily recovered by thermo-controlled separation and be efficiently reused for several cycles.
