Article
Chemistry, Multidisciplinary
Long Yang, Becky Bongsuiru Jei, Alexej Scheremetjew, Binbin Yuan, A. Claudia Stueckl, Lutz Ackermann
Summary: A copper-catalyzed electrochemical method for direct chalcogenation of o-carboranes has been established, allowing for high levels of position and chemo-selectivity control. This method provides an efficient means to activate inert cage C-H bonds for the late-stage diversification of o-carboranes.
Article
Chemistry, Multidisciplinary
Yan-Zhen Chen, Jian-Guo Fu, Xiao-Ming Ji, Shu-Sheng Zhang, Chen-Guo Feng
Summary: A new method for traceless directing cross-coupling of unreactive C(sp(3))-H bonds and azole C(sp(2))-H bonds has been described. The success of this cascade process relies on the careful selection of a bulky and electron-rich phosphine ligand, and it offers broad substrate scope, excellent regioselectivity, and good functional group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jinwon Jeon, Changseok Lee, Inyoung Park, Sungwoo Hong
Summary: This article highlights the elegant and versatile approach of chelation-assisted C-H bond and alkene functionalization using bidentate directing groups, which overcomes regiocontrol issues. The focus is on two categories of results: regioselective alkene functionalization and asymmetric C-H functionalization using chiral bidentate directing groups. Additionally, density functional theory studies are discussed to elucidate the origin of regio- and stereoselectivity induced by bidentate directing groups.
Article
Chemistry, Organic
Dianpeng Chen, Jianming Li, Xiuhua Zhang, Gongle Liu, Xin Wang, Yongwei Liu, Xuan Liu, Yingying Shan
Summary: A novel method for the synthesis of fused tetracyclic N-heterocycles is described using palladium-catalyzed cyclization of isocyanides with alkyne-tethered aryl iodides. The reaction involves a unique amino-to-alkyl 1,5-palladium migration/intramolecular C(sp(3))-C(sp(2)) coupling sequence. Isocyanide plays multiple roles in this transformation, serving as a C1 synthon, a C1N1 synthon, and the donor of C(sp(3)) for C(sp(3))-C(sp(2)) coupling, and it represents the only successful example of C(sp(3))-H activation of isocyanide.
Article
Chemistry, Organic
Olga O. Sokolova, Andrew G. Dalling, John F. Bower
Summary: This Account focuses on C-C bond activation based methodologies using minimally activated cyclopropanes, which allow for the atom economical assembly of complex scaffolds.
Article
Chemistry, Multidisciplinary
Yuya Kogure, Kohei Hatakeyama, Kai Tsuchiya, Yuta Kunii, Satoshi Ueno
Summary: This article reports the development of a novel ruthenium-catalysed cross-coupling reaction of beta-ketoamides with organoboronates. The reaction proceeds via the cleavage of the alkenyl C-N bond of the in situ generated beta-enaminoamide.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jia Qiao, Rui-Nan Ci, Qi-Chao Gan, Cheng Huang, Zan Liu, Hui-Lan Hu, Chen Ye, Bin Chen, Chen-Ho Tung, Li-Zhu Wu
Summary: The activation of the alpha-C-H bond of ketones typically requires an amine and a directing group to guide the reaction selectivity in amine-catalysis carbonyl chemistry. Here, we report the first alpha-alkylation of cyclic ketones in the absence of an amine catalyst and directing group. A direct and selective activation of the inert alpha-C-H bond of ketones chelating on the surface of colloidal quantum dots is achieved, leading to the formation of an alpha-carbon radical intermediate. This transformation opens a new way for alpha-C-H functionalization of ketones in carbonyl chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhongfeng Luo, Jingxing Jiang, Lifang Zou, Xiaoyu Zhou, Junshan Liu, Zhuofeng Ke, Fengjuan Chen, Huanfeng Jiang, Wei Zeng
Summary: The development of a Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp(2)-H functionalizations is disclosed in this study. Various readily available 2-aminopyridines and 1,2,3-triazoles can be coupled and cyclized to access polyfunctionalized azaindoles. Mechanistic studies reveal the involvement of relay carbenoid-electrophilic addition to pyridines and sequential pyridyl Csp(2)-H amination in this transformation. The post-synthetic utility of this methodology is demonstrated through versatile and site-selective modification of azaindoles.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Shuting Zhong, Xianfu Fang, Yiting Wang, Gong Zhang, Yangfeng Li, Yizhou Li
Summary: In this study, a new method for on-DNA synthesis of diverse C3-functionalized indole derivatives is presented, enabling indole-based diversification in the construction of chemical libraries.
Article
Chemistry, Multidisciplinary
Saeed Ataie, Maxwell Lohoar, Loic P. Mangin, R. Tom Baker
Summary: Three new IPr-Ag- and -Au-SNS amido and thiolate complexes were synthesized and compared to their previously reported Cu analogues as carbonyl hydroboration catalysts. Although these complexes showed no catalytic activity, treatment of the IPr-Ag-SNS amido complex with pinacolborane released N-borylated ligand, (SNSMe)-N-Me-S-Bpin, (L-1-Bpin). This finding led to reinvestigation of the IPr-Cu-SNS amido precatalyst, revealing immediate conversion of the catalyst system to [CuH(IPr)](2) upon loss of L-1-Bpin.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Alen Bjelopetrovic, Dajana Barisic, Marina Juribasic Kulcsar, Ivan Halasz, Manda Curic, Stipe Lukin
Summary: We report the mechanochemically-induced deuteration of aromatic C(sp(2))-H bonds activated by Pd at ambient temperature without the need for solvents. Deuterium was sourced from cysteine-d(4) to obtain mono- or dideuterated products from different aromatic palladacycles. Besides the high deuteration yields, we provide a detailed view of the reaction course in the solid state through time-resolved in situ Raman monitoring and DFT calculations. The obtained knowledge could lead to the broader application of this methodology for the deuteration of organic compounds.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Bubul Das, Anjali Dahiya, Ashish Kumar Sahoo, Bhisma K. Patel
Summary: The isocyanate group in aryl isocyanates acts as a transformable transient directing group, leading to the ortho olefination reaction and the formation of o-alkenylanilines. In alcoholic solvents, aryl isocyanates are converted into carbamates, initiating the insertion of acrylates via ortho C-H activation. Specifically, tAmOH serves as both a solvent and a transient directing mediator. The o-alkenylanilines are further transformed into azacoumarins and C-4 aryl-substituted azacoumarins through Pd(II)-catalyzed C-H functionalizations using aryl iodides as coupling partners.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Zhipeng Lin, Uttam Dhawa, Xiaoyan Hou, Max Surke, Binbin Yuan, Shu-Wen Li, Yan-Cheng Liou, Magnus J. Johansson, Li-Cheng Xu, Chen-Hang Chao, Xin Hong, Lutz Ackermann
Summary: Electrochemistry, with the aid of data science and artificial intelligence, is increasingly being used for molecular synthesis. The authors have successfully utilized electrocatalyzed C-H activations for selective alkenylation in late-stage drug diversification. This approach eliminates the need for directing groups, which simplifies the synthesis process and reduces waste.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yangyang Wang, Gaorong Wu, Xiaobo Xu, Binghan Pang, Shaowen Liao, Yafei Ji
Summary: This study develops a method for the direct arylation of aliphatic ketones via Pd-catalyzed beta-C(sp(3))-H bond functionalization using 2-(aminooxy)-N,N-dimethylacetamide as a novel transient directing group (TDG), resulting in moderate to good yields. The reaction is tolerant to abundant substrate of ketones and aryl iodides, expanding the applications of TDGs.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Akanksha Singh Baghel, Anjali Aghi, Amit Kumar
Summary: The regioselective ortho-alkenylation of primary benzamides with activated olefins using a Ru(II) catalyst has been achieved, allowing the controlled introduction of olefin motifs at the ortho-position of benzamides. The success of this strategy relies on fine-tuning reaction conditions and involves a base-assisted internal electrophilic-type substitution step in the reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ashish A. Mishra, Bhalchandra M. Bhanage
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Sandip T. Gadge, Ashish Mishra, Aravind L. Gajengi, Nileshkumar V. Shahi, Bhalchandra M. Bhanage
Review
Chemistry, Applied
Dnyaneshwar D. Subhedar, Ashish A. Mishra, Bhalchandra M. Bhanage
ADVANCED SYNTHESIS & CATALYSIS
(2019)
Article
Chemistry, Inorganic & Nuclear
Vishal V. Phatake, Ashish A. Mishra, Bhalchandra M. Bhanage
INORGANICA CHIMICA ACTA
(2020)
Article
Chemistry, Multidisciplinary
Ashish A. Mishra, Bhalchandra M. Bhanage
Review
Chemistry, Medicinal
Ashish A. Mishra, Bhalchandra M. Bhanage
Summary: This review summarizes current developments in novel synthetic routes for Ruthenium tethered chiral catalyst and its derivatives, along with their application in asymmetric synthesis.
Article
Chemistry, Multidisciplinary
Ashish A. Mishra, Bhalchandra M. Bhanage
Summary: The utilization of Ru-tethered-TsDPEN as a chiral catalyst in the presence of DMAB allows for the selective synthesis of optically active alpha-substituted alcohols. This catalytic system shows higher yield and enantiomeric excess compared to others, especially for ortho substituted derivatives.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Ashish A. Mishra, Shivkumar R. Chaurasia, Bhalchandra M. Bhanage
NEW JOURNAL OF CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Ashish A. Mishra, Bhalchandra M. Bhanage
NEW JOURNAL OF CHEMISTRY
(2019)
