Article
Chemistry, Physical
Yumiao Ma, Aqeel A. Hussein
Summary: We present a strategy to tune the catalytic behavior of the pincer-Co catalyst by investigating the effect of partners such as (18-crown-6)K+, W(CO)(3), and W(PMe3)(3) on the nitrile hydroboration reaction. The partner's influence on the cobalt center's electron-richness and the donor ability of the pincer ligand is revealed through pi-coordination. These findings suggest a notable partner effect that can be explored by experimentalists to tune the reactivity of catalysts without ligand modification.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Applied
Natalia S. Soldatova, Artem V. Semenov, Kirill K. Geyl, Sergey V. Baykov, Anton A. Shetnev, Anna S. Konstantinova, Mikhail M. Korsakov, Mekhman S. Yusubov, Pavel S. Postnikov
Summary: A method for copper-catalyzed N-arylation of diverse oxadiazolones using diaryliodonium salts has been reported with high yields up to 92%. It was found that the steric effects in aryl moieties determined the chemoselectivity of arylations. Mesityl-substituted diaryliodonium salts demonstrated high potential as selective arylation reagents.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Irene Martin, Cristina Aragoncillo, Pedro Almendros
Summary: This research has achieved a selective palladium-catalyzed reaction sequence, leading to the synthesis of novel 2-iodo-1-aryl-9H-carbazoles. The observed formation of 2-iodocarbazoles in contrast to gold catalysis suggests a metal-controlled cyclization through chemo- and regioselective alkyl migration and iodonium migration.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Chengyao Kimmy Cao, Niu Yaru, Jiang Yunchen, Qu Hongmei, Chen Chao
Summary: In this study, a new method for synthesizing difluoroethyl compounds was developed through a palladium-catalyzed chlorodifluoroethylation reaction. Furthermore, difluorovinylated acetanilide products were obtained through an elimination reaction.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jiajin Zhao, Guoxiong Xu, Xue Wang, Jiren Liu, Xiang Ren, Xin Hong, Zhan Lu
Summary: A cobalt-catalyzed multipositional isomerization of conjugated dienes using an 8-oxazoline iminoquinoline ligand has been reported. This reaction is simple and efficient, yielding disubstituted 1,3-dienes with good yields and stereoselectivity.
Article
Chemistry, Multidisciplinary
Yaru Niu, Chengyao Kimmy Cao, Chenxin Ge, Hongmei Qu, Chao Chen
Summary: In this study, a simple and efficient method for directly introducing a chlorodifluoroethyl group into aromatic molecules of various aromatic amides is reported. A new 2-chloro,2,2-difluoroethyl(mesityl)iodonium salt (CDFI) is used in this method. Furthermore, the chlorodifluoroethyl compounds can be smoothly converted into difluorovinyl compounds and serve as a stable source of difluorovinyl compounds with HCl-mask.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Thomas Rossolini, Ashis Das, Stefano Nicolai, Jerome Waser
Summary: A Pd-catalyzed method using a molecular tether was developed for olefin difunctionalization, enabling the simultaneous introduction of oxygen and nitrogen heteroatoms across unsaturated carbon-carbon bonds. Good yields and high diastereoselectivity were achieved with aryl-substituted alkenes, while nonterminal alkyl-substituted olefins gave aza-Heck products. Cleavage of the tether under mild conditions allowed for quick access to functionalized alcohols.
Article
Chemistry, Organic
Thomas Rossolini, Ashis Das, Stefano Nicolai, Jerome Waser
Summary: A Pd-catalyzed method based on a molecular tether has been developed for olefin difunctionalization. Oxygen and nitrogen heteroatoms were introduced across unsaturated carbon-carbon bonds simultaneously under oxidative conditions, facilitated by a trifluoroacetaldehyde-derived tether. Good yields and high diastereoselectivity were achieved with aryl-substituted alkenes, while nonterminal alkyl-substituted olefins gave aza-Heck products. Cleavage of the tether provided access to functionalized alcohols under mild conditions.
Article
Chemistry, Organic
Km Ishu, Dharmendra Kumar, Naveen Kumar Maurya, Suman Yadav, Dhananjay Chaudhary, Malleswara Rao Kuram
Summary: A palladium-catalyzed domino Heck/intermolecular direct hetero arylation sequence of unactivated alkenes was developed in this study, providing bisheterocycles bearing all-carbon quaternary centers with 1,2,3-triazole moiety in yields of 25-90%. The protocol was also successfully extended to 1,3,4-oxadiazoles, and the installed triazole was further utilized for late-stage functionalizations, with mechanistic studies pointing towards the involvement of C-H activation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Organic
Xuemei Yin, Shanshan Li, Kun Guo, Lei Song, Xiaoling Wang
Summary: Palladium-catalyzed asymmetric hydrofunctionalization of alkenes is a powerful method to obtain valuable enantioenriched molecules from cheap and readily available feedstocks, but it also faces certain challenges and opportunities.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Pran Gobinda Nandi, Raksh Vir Jasra, Akshai Kumar
Summary: Translation: The synthesis and characterization of three NNN pincer-Ru complexes based on bis(imino)pyridine ligands have been reported. These complexes, along with other previously reported pincer-Ru catalysts, have been used for the selective methylation of 2-phenylethanol and 1-phenylethanol. The most efficient catalyst was found to be [(MeBim2NNN)RuCl(PPh3)2]Cl based on the dimethyl-substituted 2,6-bis(benzimidazol-2-yl)pyridine ligand. The developed synthetic protocol is generic and can be applied to about 35 substrates. Mechanistic studies revealed that the reaction is catalyzed by well-defined molecular catalysts, and the rate-determining step is the dehydrogenolysis involving s-bond metathesis of methanol with the Ru-H species.
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Chemistry, Physical
Dennis Verspeek, Sebastian Ahrens, Anke Spannenberg, Xiaodong Wen, Yong Yang, Yong-Wang Li, Kathrin Junge, Matthias Beller
Summary: A practical manganese(ii) catalyst system with an in situ generating method, using a commercially available bis(2-picolyl) amine ligand, enables efficient epoxidation of terminal aliphatic olefins with tert-butyl hydroperoxide as the oxidant. Crystallization experiments revealed the formation of two manganese solvent complexes with MeCN and H2O, respectively. Furthermore, a detailed investigation of the quinoline additive identified its crucial role in promoting the epoxide formation while negatively affecting its stability.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Inorganic & Nuclear
Allan J. J. Canty, Alireza Ariafard
Summary: Density functional theory was employed to study the mechanistic of the oxidation of pincer complex Pd-II(mer-NCN)(K-1-O2CPh) by diphenyliodine(III) triflate in the presence of bicarbonate base. The results suggest that concerted oxidative addition by Ph2I(OCO2H) is favored over a Ph+ transfer mechanism to initially form octahedral PhPdIV(mer-NCN)(K-1-O2CPh){I(Ph)(& BULL;& BULL;& BULL;OCO2H)-I}. Interaction of bicarbonate with the iodine center has little impact on the concerted transition state but disrupts the Ph+ transfer mechanism.
Article
Chemistry, Medicinal
Gergana Popova, Marcus J. G. W. Ladds, Lars Johansson, Aljona Saleh, Johanna Larsson, Lars Sandberg, Sara Haggblad Sahlberg, Weixing Qian, Hjalmar Gullberg, Neeraj Garg, Anna-Lena Gustavsson, Martin Haraldsson, David Lane, Ulrika Yngve, Sonia Lain
JOURNAL OF MEDICINAL CHEMISTRY
(2020)
Article
Chemistry, Organic
Xingguo Jiang, Denise Meyer, Dominik Baran, Miguel A. Cortes Gonzalez, Kalman J. Szabo
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Zhiyao Zheng, Angela van der Werf, Marie Deliaval, Nicklas Selander
Article
Chemistry, Organic
Oriana Brea, Kalman J. Szabo, Fahmi Himo
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Qiang Wang, Marvin Lubcke, Maria Biosca, Martin Hedberg, Lars Eriksson, Fahmi Himo, Kalman J. Szabo
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Sybrand J. T. Jonker, Ramasamy Jayarajan, Tautvydas Kireilis, Marie Deliaval, Lars Eriksson, Kalman J. Szabo
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Qiang Wang, Maria Biosca, Fahmi Himo, Kalman J. Szabo
Summary: The electrophilic fluorination of geminal alkyl substituted vinyl-Bmida derivatives proceeds via a bora-Wagner-Meerwein rearrangement, with the Bmida group having a larger migration aptitude than the alkyl moiety. This rearrangement occurs with a low activation barrier via a bora-cyclopropane shaped transition state according to DFT modelling studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ramasamy Jayarajan, Tautvydas Kireilis, Lars Eriksson, Kalman J. Szabo
Summary: In this study, a variety of aliphatic, aromatic, and heterocyclic boronic acids were successfully modified using trifluorodiazoethane and BINOL derivatives, resulting in the synthesis of chiral trifluoromethyl containing boronic acid derivatives. The conversion of the chiral boronic acids to other compounds in situ was also demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Qiang Wang, Lars Eriksson, Kalman J. Szabo
Summary: Homologation of trisubstituted fluoroalkenes followed by allylboration of aldehyde, ketone and imine substrates is a suitable method for the synthesis of beta-fluorohydrin and amine products. With the presence of (R)-iodo-BINOL catalyst, enantioselectivities up to 99% can be achieved by formation of a single stereoisomer with adjacent stereocenters, one of which is a tertiary C-F center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marie Deliaval, Ramasamy Jayarajan, Lars Eriksson, Kalman J. Szabo
Summary: We have developed a new three-component catalytic coupling reaction involving alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. This reaction exhibits remarkably high enantio- and diastereoselectivity, leading to the formation of tertiary CF3-allenols with up to three contiguous stereocenters in a single step. The reaction proceeds under mild, neutral, and metal-free conditions, making it highly functional group tolerant.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Linpeng Liu, Yanyu Jian, Weigao Hu, Shaohu Zhao, Zhang-Jie Shi, Nicklas Selander, Taigang Zhou
Summary: A method for radical cyclization and ring-opening of oxime esters with diselenides has been developed. Both Ni(0) and Fe(ii) catalysts can be used for the selenylation of olefin-containing and cyclic oxime ester derivatives. Using this method, a variety of functionalized pyrrolines and alkyl nitriles can be synthesized in good yields. Additionally, a mechanism involving iminyl radical and carbon-centered radical intermediates has been proposed.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Denise N. Meyer, Miguel A. Cortes Gonzalez, Xingguo Jiang, Linus Johansson-Holm, Monireh Pourghasemi Lati, Mathias Elgland, Patrik Nordeman, Gunnar Antoni, Kalman J. Szabo
Summary: A new method for fluorine-18 labelling of trifluoromethyl ketones has been developed, involving the conversion of an α-COCF3 functional group to a difluoro enol silyl ether followed by halogenation and fluorine-18 labelling. The utility of this method was demonstrated by synthesizing fluorine-18 labelled neutrophil elastase inhibitors, potentially useful for detecting inflammatory disorders.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Marvin Luebcke, Kalman J. Szabo
Summary: Diazocarbonyl compounds are utilized as substrates for di- and trifunctionalization reactions involving F/CF3/SCF3 introduction, with majority of reactions based on rhodium catalysis and involving oxygen nucleophiles. The oxyfluorination reactions have been further developed for new fluorine-18 labeling method, while an arylation-trifluoromethylthiolation reaction proceeds via a Hooz-type mechanism instead of rhodium catalysis.
Article
Chemistry, Multidisciplinary
Miguel A. Cortes Gonzalez, Xingguo Jiang, Patrik Nordeman, Gunnar Antoni, Kalman J. Szabo
CHEMICAL COMMUNICATIONS
(2019)
Article
Chemistry, Multidisciplinary
Marvin Lubcke, Dina Bezhan, Kalman J. Szabo
