7568-93-6Relevant academic research and scientific papers
Application of an Electrochemical Microflow Reactor for Cyanosilylation: Machine Learning-Assisted Exploration of Suitable Reaction Conditions for Semi-Large-Scale Synthesis
Sato, Eisuke,Fujii, Mayu,Tanaka, Hiroki,Mitsudo, Koichi,Kondo, Masaru,Takizawa, Shinobu,Sasai, Hiroaki,Washio, Takeshi,Ishikawa, Kazunori,Suga, Seiji
, p. 16035 - 16044 (2021/09/02)
Cyanosilylation of carbonyl compounds provides protected cyanohydrins, which can be converted into many kinds of compounds such as amino alcohols, amides, esters, and carboxylic acids. In particular, the use of trimethylsilyl cyanide as the sole carbon source can avoid the need for more toxic inorganic cyanides. In this paper, we describe an electrochemically initiated cyanosilylation of carbonyl compounds and its application to a microflow reactor. Furthermore, to identify suitable reaction conditions, which reflect considerations beyond simply a high yield, we demonstrate machine learning-assisted optimization. Machine learning can be used to adjust the current and flow rate at the same time and identify the conditions needed to achieve the best productivity.
Catalyst-Free Electrophilic Ring Expansion of N-Unprotected Aziridines with α-Oxoketenes to Efficient Access 2-Alkylidene-1,3-Oxazolidines
Chen, Xingpeng,Huang, Zhengshuo,Xu, Jiaxi
, p. 3098 - 3108 (2021/05/10)
2-(2-Oxoalkylidene)-1,3-oxazolidine derivatives were synthesized in good to excellent yields regiospecifically through the catalyst-free electrophilic ring expansion of N-unprotected aziridines and the ketene C=O double bond of α-oxoketenes, in situ generated from the microwave-assisted Wolff rearrangement of 2-diazo-1,3-diketones. The ring expansion predominantly underwent an SN1 process and the hydrogen bond decides the (E)-configuration of products. (Figure presented.).
Enantioselective Aminohydroxylation of Styrenyl Olefins Catalyzed by an Engineered Hemoprotein
Cho, Inha,Prier, Christopher K.,Jia, Zhi-Jun,Zhang, Ruijie K.,G?rbe, Tamás,Arnold, Frances H.
, p. 3138 - 3142 (2019/02/01)
Chiral 1,2-amino alcohols are widely represented in biologically active compounds from neurotransmitters to antivirals. While many synthetic methods have been developed for accessing amino alcohols, the direct aminohydroxylation of alkenes to unprotected, enantioenriched amino alcohols remains a challenge. Using directed evolution, we have engineered a hemoprotein biocatalyst based on a thermostable cytochrome c that directly transforms alkenes to amino alcohols with high enantioselectivity (up to 2500 TTN and 90 % ee) under anaerobic conditions with O-pivaloylhydroxylamine as an aminating reagent. The reaction is proposed to proceed via a reactive iron-nitrogen species generated in the enzyme active site, enabling tuning of the catalyst's activity and selectivity by protein engineering.
Nitration-Peroxidation of Alkenes: A Selective Approach to β-Peroxyl Nitroalkanes
Chen, Yuanjin,Ma, Yangyang,Li, Liangkui,Jiang, Hao,Li, Zhiping
, p. 1480 - 1483 (2019/02/26)
Nitration-peroxidation of alkenes for the synthesis of β-peroxyl nitroalkanes has been developed by using tert-butyl nitrite and tert-butyl hydroperoxide. The method presents a new and selective difunctionalization of alkenes to introduce a nitro group and a peroxyl group across the double bonds of alkenes under mild conditions. A radical reaction pathway is proposed by experimental and theoretical studies.
The hydrogenation of mandelonitrile over a Pd/C catalyst: Towards a mechanistic understanding
McAllister, Mairi I.,Boulho, Cédric,McMillan, Liam,Gilpin, Lauren F.,Brennan, Colin,Lennon, David
, p. 26116 - 26125 (2019/09/09)
A carbon supported Pd catalyst is used in the liquid phase hydrogenation of the aromatic cyanohydrin mandelonitrile (C6H5CH(OH)CH2CN) to afford the primary amine phenethylamine (C6H5CH2CH2NH2). Employing a batch reactor, the desired primary amine is produced in 87% selectivity at reaction completion. Detection of the by-product 2-amino-1-phenylethanol (C6H5CH(OH)CH2NH2) accounts for the remaining 13% and closes the mass balance. The reaction mechanism is investigated, with a role for both hydrogenation and hydrogenolysis processes established.
Selective oxidation of thioanisole with hydrogen peroxide using copper complexes encapsulated in zeolite: Formation of a thermally stable and reactive copper hydroperoxo species
Yamaguchi, Syuhei,Suzuki, Akinori,Togawa, Makoto,Nishibori, Maiko,Yahiro, Hidenori
, p. 2645 - 2650 (2018/04/14)
[Cu(terpy)]2+ complexes encapsulated into Na-Y zeolite ([Cu(terpy)]2+@Y) were prepared, and their catalytic activities for the oxidation of sulfides using hydrogen peroxide were investigated. Several spectroscopic results, as well as elemental analysis, demonstrated the formation of [Cu(terpy)]2+ complexes in supercages of Y-zeolite. [Cu(terpy)]2+@Y exhibited high selectivity for the oxidation of thioanisole into methylphenylsulfoxide when H2O2 was used. The kinetic study of this oxidation at the catalyst [Cu(terpy)]2+@Y suggests that the reaction of [Cu(terpy)]2+ species with H2O2 is the rate-determining step. The oxidation of thioanisole, benzene, and 2-phenylethylamine using [[Cu(terpy)]2+@Y]?, which was prepared from the reaction between [Cu(terpy)]2+@Y and H2O2, quantitatively proceeded to methylphenylsulfoxide, phenol, and 2-amino-1-phenylethanol, respectively. The reaction of [Cu(terpy)]2+@Y and H2O2 was found to yield thermally stable but active CuII-OOH species in [Cu(terpy)]2+@Y.
In silico prioritization, synthesis and in vitro evaluation of tembamide analogs for anti-HIV activity
Gupta, Shiv,Kumar, Sanjay,Jariwala, Nisha,Bhadane, Deepali,Bhutani, Kamlesh Kumar,Kulkarni, Smita,Singh, Inder Pal
, p. 1455 - 1464 (2017/12/28)
Background: High attrition rate in late drug discovery and development stages leads to financial loss to industries and Governments. Despite the global prevalence of HIV infection and lack of promising treatment for AIDS patients, there are only a few drugs approved for the management of infected patients. There is an urgent need to discover newer anti-HIV drugs with novel mechanism of action and with efforts to reduce attrition rate in early drug discovery stages. Objective: Prioritization of reported potential anti-HIV-1 leads according to their quantitative estimation of druglikeness (QED), carcinogenicity, mutagenicity, absorption, metabolism and toxic properties. Synthesis of analogs of the best lead and evaluation of their anti-HIV-1 activity is shown. Methods: In silico anti-HIV lead prioritization was performed on a set of known anti-HIV natural products in order to obtain a lead with better druglikeness and ADMET properties. Prioritized lead tembamide and its four analogs were synthesized and their anti-HIV-1 activity was evaluated. Results: Tembamide was found to be a lead with better QED, absorption and metabolism properties and with no carcinogenicity, mutagenicity and toxic potential. (+)-Tembamide is previously reported to show potent anti-HIV-1 activity against laboratory adapted strains HIV-1IIIB (X4, subtype B) and HIV-1Ada5 (R5, subtype B) in H9 cell line. It was observed during this study that synthesized tembamide and its four analogs were weakly active against primary isolates HIV-1UG070 (X4, subtype D) and HIV-1VB59 (R5, subtype C) in TZM-bl cell line. Conclusion: The results showed that there is scope for the improvement of activity of tembamide analogs to discover a potent anti-HIV compound.
Remote C(sp3)-H Oxygenation of Protonated Aliphatic Amines with Potassium Persulfate
Lee, Melissa,Sanford, Melanie S.
supporting information, p. 572 - 575 (2017/02/10)
This letter describes the development of a method for selective remote C(sp3)-H oxygenation of protonated aliphatic amines using aqueous potassium persulfate. Protonation serves to deactivate the proximal C(sp3)-H bonds of the amine substrates and also renders the amines soluble in the aqueous medium. These reactions proceed under relatively mild conditions (within 2 h at 80 °C with amine as limiting reagent) and do not require a transition metal catalyst. This method is applicable to a variety of types of C(sp3)-H bonds, including 3°, 2°, and benzylic C-H sites in primary, secondary, and tertiary amine substrates.
Direct catalytic synthesis of unprotected 2-amino-1-phenylethanols from alkenes by using iron(II) phthalocyanine
Legnani, Luca,Morandi, Bill
supporting information, p. 2248 - 2251 (2016/02/18)
Aryl-substituted amino alcohols are privileged scaffolds in medicinal chemistry and natural products. Herein, we report that an exceptionally simple and inexpensive FeII complex efficiently catalyzes the direct transformation of simple alkenes into unprotected amino alcohols in good yield and perfect regioselectivity. This new catalytic method was applied in the expedient synthesis of bioactive molecules and could be extended to aminoetherification.
Aminohydroxylation of olefins with iminopyridinium ylides by dual Ir photocatalysis and Sc(OTf)3catalysis
Miyazawa, Kazuki,Koike, Takashi,Akita, Munetaka
, p. 7813 - 7820 (2016/11/16)
We have developed a new strategy for catalytic aminohydroxylation of olefins with an N-protected iminopyridinium ylide as the amine source. Iminopyridinium ylides N-protected with TFAc (trifluoroacetyl), Boc (tert-butoxycarbonyl), Troc (2,2,2-trichloroethoxycarbonyl), and Alloc (allyloxycarbonyl) groups serve as N-centered radical precursors when combined with fac-[Ir(ppy)3] photocatalysis and Sc(OTf)3catalysis. The dual Ir photoredox/Sc(OTf)3catalysis proves to be effective for aminohydroxylation of olefins under mild reaction conditions to provide 2-aminoalcohol derivatives bearing a primary amino group.
