Article
Chemistry, Multidisciplinary
Bidhan Ghosh, Satabdi Bera, Pintu Ghosh, Rajarshi Samanta
Summary: An efficient Rh(iii)-catalyzed strategy has been developed for the synthesis of quinoline braced cyclophane macrocycles via methyl (sp(3)) C-H functionalization, which is mild, simple, regioselective, and tolerates various functional groups with different ring sizes. The method involves C8-methyl metalation, metal-carbene formation, and migratory insertion, with high dilution not necessary and nitrogen being the only byproduct. Preliminary investigation suggests that the C-H metalation step is the rate-determining step.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Yan-Dong Zhang, Xiao-Yu Li, Qian-Kun Mo, Wen-Bin Shi, Jia-Bao Zhao, Shou-Fei Zhu
Summary: In this study, we developed new Co complexes with cyclopropane-based diphosphine ligands that can catalyze highly chemo-, regio-, and stereoselective hydroboration reactions of unsymmetrical internal alkynes. These reactions exhibit unusual regioselectivity, leading to the synthesis of trisubstituted alkenylborates and alkenes with different stereochemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Hanna Stachowiak-Dluzynska, Krzysztof Kucinski, Bozena Wyrzykiewicz, Rhett Kempe, Grzegorz Hreczycho
Summary: Vinylsilanes are versatile chemical derivatives that are increasingly being used in various synthetic transformations. In this study, a novel cobalt-catalyzed procedure was developed for the selective hydrosilylation of internal aryl-, alkyl-, and silylalkynes. The use of cobalt complexes with triazine-based PNP pincer-type ligands enabled the exclusive syn-addition of primary and secondary silanes to C=C bonds, resulting in the efficient formation of (E)-silylalkenes and vicinal disilylalkenes with excellent stereoselectivity and regioselectivity. Unlike other transition metal-catalyzed procedures, no external additives were required as hydrosilanes served as both substrates and activators.
Article
Chemistry, Organic
Bholanath Garai, Molla Rahamat Ali, Rajib Mandal, Basker Sundararaju
Summary: This study demonstrates the C(8)-selective nucleophilic cascade cyclization of quinoline N-oxide with easily derived 1,6-enyne from phenol derivatives. Various quinoline N-oxide and alkynes are found to be suitable for producing a library of quinoline N-oxide tethered cis-hydrobenzofurans with high yields and excellent functional group tolerance. The utility of the protocol has been achieved through post-synthetic modification of the cyclized product. Mechanistic studies reveal a base-assisted internal electrophilic-type substitution (BIES)-type pathway for C-H bond activation, and electrospray ionization mass spectrometry (ESI-MS) analysis confirms the formation of a key five-membered cobaltacycle.
Article
Chemistry, Organic
Bholanath Garai, Molla Rahamat Ali, Rajib Mandal, Basker Sundararaju
Summary: This study demonstrates the C(8)-selective nucleophilic cascade cyclization of quinoline N-oxide with easily derived 1,6-enyne from phenol derivatives. Various quinoline N-oxide and alkynes are suitable for producing a library of quinoline N-oxide tethered cishydrobenzofurans with high yields and excellent functional group tolerance. The protocol's utility is achieved through post-synthetic modification of the cyclized product. Mechanistic studies suggest a base-assisted internal electrophilic-type substitution (BIES)-type pathway for C-H bond activation, and electrospray ionization mass spectrometry (ESI-MS) analysis confirms the formation of a key five-membered cobaltacycle.
Article
Chemistry, Organic
Ankita Thakur, Ankit Kumar Dhiman, Sumit, Rakesh Kumar, Upendra Sharma
Summary: This research presents a Rh(III)-catalyzed selective C8-alkylation of quinoline N-oxides with maleimides and acrylates, showing good selectivity and substrate scope. The methodology was also demonstrated to be applicable for gram-scale synthesis and post-modification.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Rohit Sarthi, Rohit Kumar, Tamanna Sharma, Upendra Sharma
Summary: In this study, a concise Rh(III)-catalyzed C(sp3)-H alkylation of 8-methylquinolines with oxabenzonorbornadiene scaffolds and other strained olefins was presented. The developed catalytic methodology exhibits key features such as the retention of the oxabenzonorbornadiene skeleton, broad substrate scope, and wide-ranging functional group tolerance. Mechanistic studies revealed that the reaction proceeds through a non-radical pathway, with the five membered rhodacycle serving as the key intermediate. This is the first report on the C(sp3)-H alkylation of 8-methylquinolines with strained oxabenzonorbornadiene scaffolds (with ring retention).
Article
Chemistry, Organic
Han Gao, Wujie Wang, Xiangying Lv, Gang Lu, Yuliang Li
Summary: The mechanism of Co(iii)-catalyzed annulation of N-chlorobenzamide with styrene was computationally studied, focusing on the effects of chiral cyclopentadienyl (Cp) ligands on enantioselectivity using energy decomposition analysis (EDA). The study revealed a spin-crossover event of Co complexes in the computed energy profile, with the triplet state of Co species being favored in most intermediates and transition states. The irreversible styrene migratory insertion was identified as the enantioselectivity-determining step, with steric effects being the dominant factor for high-level enantiocontrol, emphasizing the importance of additional bulky substituents on the Cp ring of trisubstituted BINOL-Cp ligands.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Siya Le, Yihui Bai, Jiayan Qiu, Zuxiao Zhang, Hanliang Zheng, Gangguo Zhu
Summary: A Cu-catalyzed 5-endo-selective trifluoromethylcarbocyclization of ynones has been developed for the concise synthesis of trifluoromethylated cyclopentenones. The pivotal roles of carbonyl groups in the reaction have been well illustrated by experiments and density functional theory calculations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Meng-Hui Li, Xiao-Ju Si, He Zhang, Dandan Yang, Jun-Long Niu, Mao-Ping Song
Summary: An efficient cobalt-catalyzed three-component coupling reaction is disclosed, which can construct C(sp(2))-C(sp(3)) and C-O bonds in one-pot with high yields and functional group compatibility. Mechanistic studies suggest a radical process may be involved in the reaction.
Article
Chemistry, Organic
Jia-Yin Wang, Sai Zhang, Yao Tang, Shenghu Yan, Guigen Li
Summary: The Cu(I)-catalyzed annulation-halotrifluoromethylation and cyanotrifluoromethylation of enynones have been successfully developed, allowing for the construction of quaternary carbon-centered 1-indanones through multibond formations with moderate to good chemical yields. The reaction of enynones with Togni's reagent and chloro- or bromotrimethylsilane yielded halo- and CF3-containing 1-indenones, while the addition of K3PO4 as a base resulted in the formation of cyano-anchored (Z)-1-indanones as the major stereoisomeric products. This strategy exhibits excellent compatibility with a wide range of enynones.
Article
Chemistry, Organic
Linjuan Jiang, Hui Hu, Yuanhong Liu
Summary: A copper-catalyzed regioselective C-2 alkenylation of quinoline N-oxides with alkynes and pinacol diborane has been developed, providing efficient access to a wide variety of deoxygenated 2-alkenyl quinolines with good functional group tolerance, especially with unsymmetrical alkynes such as aryl(alkyl)acetylenes and enynes.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Physical
Qiaoya Zhang, Ci Chen, Bairong Liu, Yuan Liu, Yang Gao, Qian Chen, Yanping Huo, Xianwei Li
Summary: Selective C-H annulation with unsymmetrical alkynes has been a challenge, but recent advances in the development of directing groups, metal catalysts, and versatile alkynes have overcome this problem, ensuring overall regioselectivity, enantioselectivity, efficiency, and synthetic application.
Article
Chemistry, Multidisciplinary
Minghao Zhang, Zheming Liu, Wanxiang Zhao
Summary: Remote functionalization is a powerful strategy for accessing value-added functional molecules from readily available feedstocks. This study presents a catalyst for the remote borylation of alkynes, providing a new reaction mode for the synthesis of 1,n-diboronates. The synthesis of various multi-boronic esters and their selective manipulation through subsequent reactions is demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuri Saito, Jun Kikuchi, Chen Wang, Naohiko Yoshikai
Summary: We report the design and development of Co/Al and Co/Mg bimetallic catalysts supported by a phosphine/secondary phosphine oxide (PSPO) bifunctional ligand for the selective C-H alkenylation of nitrogen-containing heteroarenes with alkynes. These catalysts enable the alkenylation of pyridine, pyridone, and imidazo[1,2-a]pyridine derivatives at the C-H site proximal to the Lewis basic nitrogen or oxygen atom, with a selectivity profile distinct from previously developed cobalt-diphosphine/aluminum catalyst. The alkenylated products were obtained in moderate to good yields using various heterocycles and differently substituted internal alkynes. Kinetic isotope effect experiments suggest the irreversibility of the C-H activation step, the relevance of which to the rate-limiting step depends on the reaction conditions. Density functional theory calculations indicate that ligand-to-ligand hydrogen transfer is the common mechanism of C-H activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Deepti Kalsi, Nagaraju Barsu, Basker Sundararaju
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Article
Chemistry, Physical
Deepti Kalsi, Subhradeep Dutta, Nagaraju Barsu, Magnus Rueping, Basker Sundararaju
Article
Chemistry, Multidisciplinary
Narasinga Rao Palepu, J. Richard Premkumar, Akalesh Kumar Verma, Kaushik Bhattacharjee, S. R. Joshi, Scott Forbes, Yurij Mozharivskyj, Kollipara Mohan Rao
ARABIAN JOURNAL OF CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Balakumar Emayavaramban, Priyanka Chakraborty, Basker Sundararaju
Review
Chemistry, Physical
Vikas Dwivedi, Deepti Kalsi, Basker Sundararaju
Article
Chemistry, Multidisciplinary
Priyanka Chakraborty, Manoj Kumar Gangwar, Balakumar Emayavaramban, Eric Manoury, Rinaldo Poli, Basker Sundararaju
Article
Chemistry, Applied
Bhuttu Khan, Vikas Dwivedi, Basker Sundararaju
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Multidisciplinary
Nagaraju Barsu, Markus Leutzsch, Alois Fuerstner
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Rajib Mandal, Nagaraju Barsu, Bholanath Garai, Abir Das, Dmitry Perekalin, Basker Sundararaju
Summary: A new protocol has been developed for mono- and bis-ortho-C-H alkynylation of easily accessible benzamide derivatives using alkynyl bromides at room temperature by combining cobalt and photocatalysts. Different alkynyl bromides have shown diverse reactivity towards C-H alkynylation and competing C-H/N-H bond annulation reactions, resulting in good yields with excellent functional group tolerance.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Deepti Kalsi, Nagaraju Barsu, Sagnik Chakrabarti, Pardeep Dahiya, Magnus Rueping, Basker Sundararaju
CHEMICAL COMMUNICATIONS
(2019)
Article
Chemistry, Organic
Balakumar Emayavaramban, Priyanka Chakraborty, Eric Manoury, Rinaldo Poli, Basker Sundararaju
ORGANIC CHEMISTRY FRONTIERS
(2019)
Article
Chemistry, Physical
Nagaraju Barsu, Deepti Kalsi, Basker Sundararaju
CATALYSIS SCIENCE & TECHNOLOGY
(2018)
Article
Chemistry, Multidisciplinary
Malay Sen, Nimmakuri Rajesh, Balakumar Emayavaramban, J. Richard Premkumar, Basker Sundararaju
CHEMISTRY-A EUROPEAN JOURNAL
(2018)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
