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861.
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863.
Dr. Zhipeng Zheng Youge Pu Prof. Javier Adrio Prof. Patrick J. Walsh 《Angewandte Chemie (International ed. in English)》2023,62(25):e202303069
Aziridines are highly valued synthetic targets in organic and medicinal chemistry. The organocatalytic synthesis of such structures with broad substrate scope and good diastereoselectivity, however, is rare. Herein, we report a broadly applicable and diastereoselective synthetic method for the synthesis of trans-aziridines from imines and benzylic or alkyl halides utilizing sulfenate anions (PhSO–) as the catalyst. Substrates bearing heterocyclic aromatic groups, alkyl, and electron-rich and electron-poor aryl groups were shown to be compatible with this method (33 examples), giving good yields and high diastereoselectivities (trans : cis >20 : 1). Further functionalization of aziridines containing cyclopropyl or cyclobutyl groups was achieved through ring-opening reactions, with a cyclobutyl-substituted norephedrine derivative obtained through a four-step synthesis. We offer a mechanistic proposal involving reversible addition of the deprotonated benzyl sulfoxide to the imine to explain the high trans-diastereoselectivity. 相似文献
864.
Dr. Bowen Hu Dr. Haoqiang Zhao Yu Wu Prof. Patrick J. Walsh 《Angewandte Chemie (International ed. in English)》2023,62(23):e202300073
A novel, selective and high-yielding palladium-catalyzed carbonylative arylation of a variety of weakly acidic (pKa 25–35 in DMSO) benzylic and heterobenzylic C(sp3)−H bonds with aryl bromides has been achieved. This system is applicable to a range of pro-nucleophiles for access to sterically and electronically diverse α-aryl or α,α-diaryl ketones, which are ubiquitous substructures in biologically active compounds. The Josiphos SL-J001-1-based palladium catalyst was identified as the most efficient and selective, enabling carbonylative arylation with aryl bromides under 1 atm CO to provide the ketone products without the formation of direct coupling byproducts. Additionally, (Josiphos)Pd(CO)2 was identified as the catalyst resting state. A kinetic study suggests that the oxidative addition of aryl bromides is the turnover-limiting step. Key catalytic intermediates were also isolated. 相似文献
865.
Dr. Shengzu Duan Ya Du Lingling Wang Xun Tian Yujin Zi Prof. Dr. Hongbin Zhang Prof. Dr. Patrick J. Walsh Prof. Dr. Xiaodong Yang 《Angewandte Chemie (International ed. in English)》2023,62(19):e202300605
α-Amino nitriles are versatile structural motifs in a variety of biologically active compounds and pharmaceuticals and they serve as valuable building blocks in synthesis. The preparation of α- and β-functionalized α-amino nitriles from readily available scaffolds, however, remains challenging. Herein is reported a novel dual catalytic photoredox/copper-catalyzed chemo- and regioselective radical carbocyanation of 2-azadienes to access functionalized α-amino nitriles by using redox-active esters (RAEs) and trimethylsilyl cyanide. This cascade process employs a broad scope of RAEs and provides the corresponding α-amino nitrile building blocks in 50–95 % yields (51 examples, regioselectivity >95 : 5). The products were transformed into prized α-amino nitriles and α-amino acids. Mechanistic studies suggest a radical cascade coupling process. 相似文献
866.
John Buckeridge Keith T. Butler C. Richard A. Catlow Andrew J. Logsdail David O. Scanlon Stephen A. Shevlin Scott M. Woodley Alexey A. Sokol Aron Walsh 《ChemInform》2015,46(31):no-no
A multiscale quantum‐chemical approach is used for examining the electronic structure of eight known TiO2 polymorphs and aligning their ionization potential and electron affinity relative to an absolute energy reference. 相似文献
867.
Camilla Russo Dr. Matthew C. Leech Jamie M. Walsh Dr. Joe I. Higham Lisa Giannessi Emmanuelle Lambert Cyrille Kiaku Dr. Darren L. Poole Dr. Joseph Mason Dr. Charles A. I. Goodall Dr. Perry Devo Dr. Mariateresa Giustiniano Dr. Marco Radi Dr. Kevin Lam 《Angewandte Chemie (International ed. in English)》2023,62(38):e202309563
Hydrogenation reactions are staple transformations commonly used across scientific fields to synthesise pharmaceuticals, natural products, and various functional materials. However, the vast majority of these reactions require the use of a toxic and costly catalyst leading to unpractical, hazardous and often functionally limited conditions. Herein, we report a new, general, practical, efficient, mild and high-yielding hydrogen-free electrochemical method for the reduction of alkene, alkyne, nitro and azido groups. Finally, this method has been applied to deuterium labelling. 相似文献
868.