Article
Chemistry, Multidisciplinary
Wei Huang, Jiahui Bai, Yinlong Guo, Qinglei Chong, Fanke Meng
Summary: A catalytic enantioselective coupling of 1,1-disubstituted allenes and aldehydes is achieved through regiodivergent oxidative cyclization followed by stereoselective protonation or reductive elimination promoted by chiral phosphine-Co complexes. This unprecedented reaction pathway for Co catalysis allows for the catalytic enantioselective generation of metallacycles with divergent regioselectivity accurately controlled by chiral ligands, leading to a wide range of allylic alcohols and homoallylic alcohols in high yields and excellent regioselectivity, diastereoselectivity, and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Srimanta Manna
Summary: Copper-catalyzed enantioselective borylative cyclization is a powerful tool for generating boron-containing carbocycles and heterocycles through the difunctionalization of unsaturated hydrocarbons. This review focuses on the copper-catalyzed borofunctionalization and enantioselective cyclization of alkenes, allenes, and alkynes, as well as the current understanding of the underlying mechanisms.
Article
Chemistry, Multidisciplinary
Zhi-Kai Zhang, Ya-Li Feng, Zheng Ruan, Yuan-Qing Xu, Zhong-Yan Cao, Meng-Hua Li, Chao Wang
Summary: This article presents a practical method for 1,2-diborylation of non-activated monosubstituted alkenes via nickel catalysis. The method shows high tolerance towards functional groups and can be applied for the synthesis of drugs and modification of natural product derivatives. Preliminary mechanistic studies suggest the involvement of a Ni(ii) catalytic cycle.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Min Gao, Yongyi Li, Xuemin Li, Lin Hu
Summary: A new reaction method has been developed for the direct coupling of simple oxindoles with alkyl dihalides, leading to the synthesis of cyclopentane- and cyclohexane-fused spirooxindole scaffolds with high yields and enantioselectivities. The method utilizes general phase-transfer catalysis and shows broad applicability and mild conditions. It also enables gram-scale synthesis of the core of the drug ubrogepant in two steps.
Article
Chemistry, Organic
Zhehui Liao, Jiantao Zhang, Tongxiang Cao, Shifa Zhu
Summary: A series of highly strained bicyclo[3.n.1]alkenones have been successfully synthesized with good-to-excellent enantioselectivities and moderate-to-good yields via copper-catalyzed formal [3+3] cycloaddition. The versatile chiral cycloadducts could be selectively converted into various valuable bridge systems, showing great potential for the construction of natural and bioactive compounds containing a [3.n.1] moiety.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xi Xiao, Xiaobiao Lu, Ming Zhang, Haoqing Hou, Changfeng Wan, Jinbiao Liu
Summary: A novel synthetic method was successfully developed for the preparation of multisubstituted dihydrochromeno[2,3-b]indole derivatives in moderate to high yields using a catalytic environmentally benign iron salt.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Song Feng, Baoqi Ren, Lige Li, Fengmin Xia, Zhiyong Tang, Yu Zhang, Xiaoning Liu, Qixuan Lu, Wenge Zhong
Summary: This method achieves the N-heteroaryl-directed Ru-catalyzed asymmetric hydrogenation of α,α-disubstituted vinyl ethers with good to excellent enantioselectivities, providing an attractive approach for synthesizing pharmaceutically active heteroaryl compounds containing chiral ether units.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Huawei Lin, Xianru Yang, Wenyue Ning, Xiaofang Huang, Xiaoqun Cao, Yanqing Ge, Biming Mao, Chang Wang, Hongchao Guo, Chunhao Yuan
Summary: Nitrogen-containing heterocycles play crucial roles in biologically active natural products and pharmaceuticals, and the palladium-catalyzed decarboxylative cycloaddition reactions are powerful synthetic tools. Vinyl benzoxazinones have emerged as versatile building blocks for nitrogenous skeletons.
Article
Chemistry, Organic
Zhidong Jiang, Jianhui Zhou, Haoran Zhu, Hong Liu, Yu Zhou
Summary: A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported, generating diversely functionalized carbazole frameworks with good to excellent yields. The most notable feature is the formation of a novel [5 + 1] cyclization product, accompanied by the complete removal of acetyl and N,N-dimethyl groups from the substrates, rather than the expected [4 + 2] cyclization products.
Article
Chemistry, Organic
Xiaodong Gu, Ling Meng, Mingliang Li, Jun (Joelle) Wang
Summary: A Cu(I)/(R,R)-Ph-BPE-catalyzed enantioselective hydroamination of 2H-chromenes and 2H-thiochromenes with anthranils has been developed, allowing for efficient and atom-economical asymmetric access to a series of 4-arylamino chromanes and thiochromanes with high yields (up to 96%) and excellent enantioselectivities (up to 99% ee). These valuable chiral chromane and thiochromane products serve as key intermediates for accessing nitrogen-, oxygen- and sulfur-containing bioactive compounds with increased molecular complexity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Jing Wang, Xiaoxue Zhang, Jianhui Zhou, Liping Yan, Yuan Li, Naixuan Zhao, Hong Liu, He Huang, Yu Zhou
Summary: A Ru(ii)-catalyzed C-H activation and annulation cascade was successfully developed for the construction of coumarin-fused benzo[a]quinolizin-4-ones and pyridin-2-ones. This reaction resulted in the formation of a unique 6-6-6-6-6 pentacyclic coumarin-fused scaffold through two successive C-H bond activations and [4 + 2] annulation cascade in a one-pot operation. The resulting products exhibited good affinity for the ENL YEATS domain.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Yichuan Zhao, Jin-Lin Wang, Zhe Zhang, Xue-Song Li, Zhi-Jie Niu, Xue-Yuan Liu
Summary: This study describes a direct allenylation reaction of inactive cyclic ethers, utilizing a copper-catalyzed 1,4-difunctionalization of 1,3-enynes with cyano group installation. The methodology exhibits broad functional group compatibility to 1,3-enynes, allowing for the synthesis of diversified allene-modified cyclic ether derivatives with high regioselectivity under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yongquan Ning, Qingmin Song, Paramasivam Sivaguru, Lizuo Wu, Edward A. Anderson, Xihe Bi
Summary: In this study, we reported a silver-catalyzed reaction that enables the insertion of alkynyl carbenes into beta-ketocarbonyls, providing trisubstituted allenyl ketones. This reaction represents the first example of alkynyl carbene insertion into C-C sigma bonds, resulting in products with an sp(2) carbon center. The obtained products serve as useful substrates for further transformations.
Article
Chemistry, Organic
Jixin Pian, Qingqing Chen, Yujiao Luo, Zhifei Zhao, Jichang Liu, Lin He, Shi-Wu Li
Summary: An enantioselective cyclopropanation reaction of sulfoxonium ylides with beta,gamma-unsaturated ketoesters catalyzed by a chiral rhodium catalyst has been achieved, leading to the synthesis of various optically pure cyclopropanes.
Article
Nanoscience & Nanotechnology
Cang-Hua Zhang, Zhi-Lei Wu, Run-Xue Bai, Tian-Ding Hu, Bin Zhao
Summary: In this study, a novel copper-organic framework catalyst was developed for the cyclization reaction of aziridines with CO2. The catalyst exhibited high selectivity, excellent chemical stability, and a record-breaking turnover number. The mechanism of the reaction was elucidated through NMR, isotope labeling experiments, and density functional theory calculations, revealing the synergistic catalytic effect of the catalyst and TBAB.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Inorganic & Nuclear
Yang-Yun Chu, Annabelle Lolinco, Naresh Eedugurala, Arkady Ellern, Theresa L. Windus, Aaron D. Sadow
Summary: The study investigates the reactions of proligands C(5)H(5)CMe(2)CHPhOx(R) (R = Me-2, CHMe2, and CMe3) with M(NMe2)(4) (M = Ti, Zr, and Hf), and identifies different reaction products under different conditions and with different ligands and metal centers. The results highlight the importance of the oxazoline ligand in the reaction and its effects on the proton transfer.
Article
Chemistry, Multidisciplinary
Zachery Crandall, Kevin Basemann, Long Qi, Theresa L. Windus
Summary: The automation of chemical reactions in research and development can reduce costs and waste generation, enhancing efficiency. Rxn Rover, an open-source, modular automation platform, helps research groups with reaction discovery and optimization. Through its plugin architecture, reaction optimization and control can be achieved to save time and resources.
REACTION CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Applied
Ellie L. Fought, Yong Han, Theresa L. Windus, Igor I. Slowing, Takeshi Kobayashi, James W. Evans
Summary: New strategies are proposed for generating models of linear nanopores in amorphous silica with surface structures that match experimental observations. These models successfully target the overall density of surface silanol groups, as well as the proportion of geminal versus mono silanols, for which additional experimental NMR data is provided. The strategies include pore drilling in bulk amorphous silica and cylindrical resist methodology to form amorphous silica around a cylindrical exclusion region, followed by dehydroxylation and hydroxylation processes. Tailoring of these processes is necessary to achieve the desired proportion of geminals.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Uddhav Kanbur, Alexander L. Paterson, Jessica Rodriguez, Andrew L. Kocen, Ryan Yappert, Ryan A. Hackler, Yi-Yu Wang, Baron Peters, Massimiliano Delferro, Anne M. LaPointe, Geoffrey W. Coates, Frederic A. Perras, Aaron D. Sadow
Summary: The C-H/Et-Al exchange reaction of saturated hydrocarbons and AlEt3 using zirconium catalysts produces versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(OtBu)(4) on silica/alumina provides monopodal SiO-Zr(OtBu)(3) surface pre-catalyst sites that can be activated by ligand exchange with AlEt3. This selective methyl group alumination enables the C-H alumination of various hydrocarbon substrates without significant chain deconstruction. Additionally, methane can undergo selective mono-alumination under solvent-free catalytic conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Katherine E. McCullough, Ian L. Peczak, Robert M. Kennedy, Yi-Yu Wang, James Lin, Xun Wu, Alexander L. Paterson, Frederic A. Perras, Jacklyn Hall, A. Jeremy Kropf, Ryan A. Hackler, Youngho Shin, Jens Niklas, Oleg G. Poluektov, Jianguo Wen, Wenyu Huang, Aaron D. Sadow, Kenneth R. Poeppelmeier, Massimiliano Delferro, Magali S. Ferrandon
Summary: This study presents a scalable synthesis method for Pt/STO by surface organometallic chemistry (SOMC) techniques using Pt(ii) acetylacetonate or trimethyl(methylcyclopentadienyl)platinum. The Pt/STO catalysts effectively hydrogenolyzed polyolefins into hydrocarbon oils, offering a promising approach for upcycling plastic waste. This new synthesis method overcomes the cost and resource-intensive issues associated with the previous atomic layer deposition (ALD) technique.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Inorganic & Nuclear
Rahul Kalita, Wahida Begum, Poorvi Gupta, Manav Chauhan, Naved Akhtar, Rajashree Newar, Kuntal Manna
Summary: This research reports on the synthesis and characterization of an aluminum metal-organic framework node-supported copper(II) chloride catalyst, which efficiently oxidizes alkenes to carbonyl or diol compounds using H2O2 as an oxidizing agent. The catalyst exhibits excellent selectivity and can be recycled, highlighting the importance of MOF-supported metal catalysts for oxidation reactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Neha Antil, Manav Chauhan, Naved Akhtar, Rahul Kalita, Kuntal Manna
Summary: The direct conversion of methane to acetic acid in a one-step reaction is a industrially important method. Researchers have discovered that by using a metal-organic framework catalyst with a copper hydroxyl site, methane can be oxidized to acetic acid using molecular oxygen under mild conditions. This study is significant for the design of low-cost and environmentally friendly catalysts for the conversion of methane to acetic acid and other valuable chemicals.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Shaojiang Chen, Akalanka Tennakoon, Kyung-Eun You, Alexander L. L. Paterson, Ryan Yappert, Selim Alayoglu, Lingzhe Fang, Xun Wu, Tommy Yunpu Zhao, Michelle P. P. Lapak, Mukunth Saravanan, Ryan A. A. Hackler, Yi-Yu Wang, Long Qi, Massimiliano Delferro, Tao Li, Byeongdu Lee, Baron Peters, Kenneth R. R. Poeppelmeier, Salai C. C. Ammal, Clifford R. R. Bowers, Frederic A. Perras, Andreas Heyden, Aaron D. D. Sadow, Wenyu Huang
Summary: Non-reducible zirconia catalysts can efficiently hydrogenolytically cleave polyolefins, achieving similar activity as precious metal nanoparticles.
Article
Chemistry, Inorganic & Nuclear
Yang-Yun Chu, Andres Garcia Alejo, Sergey L. Bud'ko, Kasuni Boteju, Smita Patnaik, Arkady Ellern, Marilu Perez Garcia, Aaron D. Sadow
Summary: The magnetic properties of 4f organometallic compounds stabilized by secondary Ln-H-Si and benzylic interactions were investigated. The compounds without a benzyl group have a larger ligand field splitting energy manifold. Doping DyR3 into LaR3 results in the crystal structure of the latter compound, and the resulting material shows hysteresis in magnetic measurements.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Naved Akhtar, Manav Chauhan, Bharti Rana, Chhaya Thadhani, Rahul Kalita, Wahida Begum, Biplab Ghosh, Kuntal Manna
Summary: This study reports a catalyst supported by a zirconium metal-organic framework, which shows excellent catalytic activity and a broad substrate scope for the selective reduction of nitro compounds using phenylsilane as a reducing agent under mild conditions. The catalyst exhibits good tolerance towards diverse functional groups and can be recycled for multiple cycles.
Article
Materials Science, Multidisciplinary
Chandan Bhogendra Jha, Chitrangda Singh, Raunak Varshney, Sweta Singh, Kuntal Manna, Rashi Mathur
Summary: This study synthesizes amino acid-based MOF using l-aspartic acid and calcium, and optimizes the reaction conditions. Despite low porosity and surface area, the Ca-MOF shows high impact on haemostatic property. It has the shortest clotting time and lowest blood loss in a rat-tail amputation model, suggesting its potential as a safe and effective haemostatic agent.
MATERIALS ADVANCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Naved Akhtar, Manav Chauhan, Poorvi Gupta, Neha Antil, Kuntal Manna
Summary: This study presents a practical and environmentally friendly method for the synthesis of formamides through N-formylation of amines using CO2 as a cheap and non-toxic C1-feedstock and hydrosilane reducing agent. The use of a porous metal-organic framework-supported cobalt catalyst allows for efficient and chemoselective mono-N-formylation of a wide range of aliphatic and aromatic amines under mild conditions. The catalyst exhibits good tolerance towards various functional groups and can be recycled multiple times.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Max Meirow, Akalanka Tennakoon, Xun Wu, Jarod Willmon, Daniel Howell, Wenyu Huang, Aaron D. Sadow, Erik Luijten
Summary: Due to the plastic waste crisis, selective chemical upcycling of polyolefins into value-added products has attracted great interest. A recent study has synthesized a catalytic architecture that can control the product chain lengths by manipulating the pore length, and uncovered the dynamic phenomenon responsible for the pore-length dependence of the cleavage products.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Neha Antil, Manav Chauhan, Naved Akhtar, Rajashree Newar, Wahida Begum, Jaideep Malik, Kuntal Manna
Summary: In this study, a novel Ce-UiO-Co heterogeneous catalyst is reported, which can efficiently convert methane to methanol under mild conditions with high selectivity and yield. The catalyst design is based on a metal-organic framework and involves the formation of an intermediate species in the pores of Ce-UiO-66, enabling the activation and functionalization of methane.
Article
Chemistry, Physical
Rajashree Newar, Rahul Kalita, Naved Akhtar, Neha Antil, Manav Chauhan, Kuntal Manna
Summary: A single-site cobalt(ii) hydride catalyst supported on an aluminum metal-organic framework (DUT-5-CoH) is capable of efficiently transforming amines into the corresponding N-formamides, with high catalytic activity and recyclability.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)