Review
Chemistry, Organic
Ruchi Sharma, M. Ramu Yadav
Summary: Decarboxylative coupling reactions using readily available (hetero)aryl carboxylic acids are an efficient approach for forming new C-C and C-X bonds, with the advantage of eliminating CO2 as a by-product and being more environmentally friendly. This review summarizes recent developments in ipso-decarboxylative C-X bond formations using (hetero)aryl carboxylic acids, and highlights current limitations and future research opportunities in aryl-decarboxylative coupling reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Jing Zhang, Ye-Xing Hou, Yan-Liu Tang, Ji-Hang Xu, Zi-Kui Liu, Yang Gao, Xiao-Qiang Hu
Summary: This convenient DMAP-catalysed decarboxylative amination allows for the sustainable synthesis of a wide range of aryl and alkyl amines in useful to good yields without the use of any activating reagent or external oxidant under transition-metal-free conditions. The synthetic potential of this methodology is demonstrated through late-stage modification of bioactive acids and concise synthesis of carbamate and ureas.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Zhuang Ma, Zhilong Chen
Summary: This study presents a tungstate-catalyzed decarboxylative halogenation of phenolic acids, which can be used to prepare antibiotic bromophene and its analogues. Mechanistic studies suggest that the reaction may proceed through either halogenation-decarboxylation or decarboxylation-halogenation pathway. In addition, chloride ions have an influence on the selectivity of halide in this reaction.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Organic
Mo Yu, Kaikai Niu, Ziwen Wang, Yuxiu Liu, Qingmin Wang
Summary: This study presents a protocol for visible-light-induced perfluoroalkylation reactions of aryl acrylic acids, which is important for late-stage modification of biologically active molecules. The reactions proceed in a decarboxylative manner using perfluoroalkyl iodides as radical precursors and inexpensive eosin Y as a photocatalyst. The easy accessibility of perfluoroalkyl iodides and the broad substrate scope, mild conditions, and metal-free catalyst make this protocol applicable for transforming inexpensive raw materials to high-value chemicals.
Article
Chemistry, Organic
James Murray, Maria V. Silva Elipe, Kyle D. Baucom, Derek B. Brown, Kyle Quasdorf, Seb Caille
Summary: The ipso nitration of aryl boronic acid derivatives using fuming nitric acid has been developed, providing an efficient and chemoselective approach to various aromatic nitro compounds. This study reveals that the activation agents and nitro sources reported in the literature likely generate a common active reagent, anhydrous HNO3, with kinetic and mechanistic studies indicating that the (NO2)-N-center dot radical is the active species.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bo Jin, Ariamala Gopalsamy, Bo Peng, Li Sha, Sharon Tentarelli, Lakshmaiah Gingipalli
Summary: A photoredox-catalyzed decarboxylative addition of N-substituted acetic acids to aldehydes was developed for the synthesis of secondary alcohols. The successful implementation of this methodology relies on the use of protic solvents. This strategy allows the formation of a novel C-C bond between aldehydes and weakly nucleophilic and medicinally relevant heteroaryls such as indoles, pyrroles, indazoles, and azaindoles.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nianxin Rong, Yongsheng Yuan, Huijie Chen, Changguang Yao, Teng Li, Yantao Wang, Weiran Yang
Summary: A simple and practical procedure for synthesizing 2-iodoanilines has been developed, with highly regioselective products obtained in satisfactory to good yields using inexpensive halogen donors. Oxygen was found to be necessary for the transformation, and control experiments suggested a radical pathway involved. The procedure is operationally scalable and exhibits high functional-group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
Tharique N. Ansari, Sudripet Sharma, Susanta Hazra, Frederick Hicks, David K. Leahy, Sachin Handa
Summary: A micelle-enabled catalytic carboxylation of (hetero)aryl halides has been developed, utilizing aqueous micelles to stabilize reactive carbanions and single-metal atom catalysts. Mechanistic analyses support a carbanion pathway, and the method shows broad substrate tolerance and is applied to the synthesis of isotopically enriched carboxylic acids.
Article
Chemistry, Organic
Valeriia Hutskalova, Farhan Bou Hamdan, Christof Sparr
Summary: An efficient methodology for the photoredox- and nickel-catalyzed aminocarbonylation of (hetero)aryl bromides was developed using readily available oxamic acids and a widely used organic photoredox catalyst. This transformation provides an attractive alternative to classical amidation procedures, with mild reaction conditions.
Article
Chemistry, Multidisciplinary
Viet D. Nguyen, Graham C. Haug, Samuel G. Greco, Ramon Trevino, Guna B. Karki, Hadi D. Arman, Oleg V. Larionov
Summary: A direct decarboxylative sulfinylation reaction was developed, enabling the conversion of carboxylic acids to sulfoxides. This reaction improves the structural diversity of synthetically accessible sulfoxides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zezhong Gao, Hang Wang, Chunlin Zhou, Ning Wang, Shangda Li, Gang Li
Summary: In this study, a new C-H functionalization method was reported for the remote site-selective C-H iodination via C(sp(2))-H/C(sp(2))-I metathesis. The mild iodinating reagent, 1-iodo-4-methoxy-2-nitrobenzene, was used to iodinate 2-aryl benzoic acid derivatives, including 2-(naphthalen-1-yl)benzoic acids and [1,1'-binaphthalene]-2-carboxylic acids, giving valuable iodinated products in a site- and chemo-selective manner.
Article
Chemistry, Organic
Biquan Xiong, Lulu Si, Longzhi Zhu, Yu Liu, Weifeng Xu, Ke-Wen Tang, Shuang-Feng Yin, Peng-Cheng Qian, Wai-Yeung Wong
Summary: A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis-Arbuzov rearrangement is reported. The reaction can be carried out effectively without the use of a ligand and a base. Various aryl acrylic acids and P(III)-nucleophiles are compatible in this transformation, providing β-keto-organophosphorus compounds with good to excellent yields. The possible mechanism and kinetic studies show that this transformation may proceed through second-order chemical kinetics and involves a radical process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sangeth Jenthra, Totan Mondal, Gregor Kemper, Marcus Lantzius-Beninga, Markus Hoelscher, Walter Leitner
Summary: A highly chemo- and regioselective decarboxylative Heck-type coupling of carboxylic acids and terminal olefins was achieved using a catalytic system composed of Pd(OAc)(2) in the presence of phosphine-sulfonamido ligands. The bulky ligand L1 favored the formation of 1,1-disubstituted branched olefins with high selectivity, while the less bulky ligand L2 resulted in the formation of 1,2-disubstituted linear products in high yield. Detailed mechanistic investigation revealed that the aryl substituent at the sulfonamide group of ligand L1 favored 1,2-insertion, while the less bulky ligand L2 favored 2,1-insertion.
Article
Chemistry, Organic
Han Ding, Ningjie Yan, Peng Wang, Ni Song, Qikai Sun, Tiantian Li, Ming Li
Summary: An efficient protocol for organophotocatalytic synthesis of reverse glycosyl fluorides (RGFs) has been established using 9-mesityl-10-methyl-acridinium (Mes-Acr(+))-mediated oxidative decarboxylative fluorination of uronic acids. Both pentofuranoid and hexopyranoid uronic acids can serve as viable substrates for this transformation, and a wide range of functional groups are tolerated. The potential of this reaction is demonstrated by the convenient synthesis of RGF-type nucleosides, particularly those with a unique l-lyxo-configuration, thereby providing a novel method to expand the chemical space of nucleosides widely used in drug discovery and development.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Xiangtai Meng, Hehua Xu, Yu Zheng, Jinyue Luo, Shenlin Huang
Summary: A new method has been developed for the synthesis of carbonyl compounds from aliphatic carboxylic acids through electrochemical decarboxylative oxygenation, which features excellent substrate compatibility and high yields of ketones, aldehydes, and amides.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Physical
Xingao Zhang, Felix N. Castellano
Summary: Researchers successfully addressed the challenge of observing TADPL in InP QDs caused by electron trap states by using the heterocyclic aromatic compound QCA. They found that QCA-functionalized InP QDs can generate bright-state TADPL through energy transfer between photoexcited InP QDs and surface-anchored QCA chromophores.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Nanoscience & Nanotechnology
Ankit Dara, Derek M. Mast, Anton O. Razgoniaev, Cory E. Hauke, Felix N. Castellano, Alexis D. Ostrowski
Summary: This study used a luminescent complex as an optical probe to monitor real-time viscosity changes in various adhesives during the curing process. The emission lifetime was found to accurately reflect changes in viscosity, and this method was applicable to opaque samples.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Materials Science, Multidisciplinary
Rishabh D. Guha, Evgeny O. Danilov, Katherine Berkowitz, Oluwatimilehin Oluwajire, Landon R. Grace
Summary: Moisture absorption contributes to the performance degradation of epoxy-based polymer materials. The state of water molecules in crosslinked epoxy depends on their bonding interactions and local environment, which can be controlled through experimental curing schedule. This study investigated different network architectures of crosslinked epoxy matrices cured with varying epoxy:hardener ratios. The correlation between moisture absorption, network morphology, and dielectric properties was established using IR spectroscopy and dielectric readings.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Denis Leshchev, Andrew J. S. Valentine, Pyosang Kim, Alexis W. Mills, Subhangi Roy, Arnab Chakraborty, Elisa Biasin, Kristoffer Haldrup, Darren J. J. Hsu, Matthew S. Kirschner, Dolev Rimmerman, Matthieu Chollet, J. Michael Glownia, Tim B. van Driel, Felix N. Castellano, Xiaosong Li, Lin X. X. Chen
Summary: The trajectories of photoexcited molecules before thermalization play a crucial role in determining the outcome of photochemical reactions. By using femtosecond wide-angle X-ray solution scattering, the excited-state trajectories of a diplatinum complex with photoactivated metal-metal sigma-bond formation and Pt-Pt stretching motions were observed in real time. The observed motions coincide with the coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. The identification of two key coordinates for intersystem crossing provides insights into the electronic transitions occurring on the time scales of measured vibrational motions, revealing ultrafast nonadiabatic or nonequilibrium processes involving multiple excited-state potential energy surfaces (PESs).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Michael C. Rosko, Eli M. Espinoza, Sarah Arteta, Sarah Kromer, Jonathan P. Wheeler, Felix N. Castellano
Summary: In this study, four new copper(I) coordination complexes were synthesized and characterized. These complexes exhibit longer excited-state lifetimes and high photoluminescence quantum efficiencies. By adjusting the 2,9-substituents, the photophysical properties of these complexes can be tailored, providing new directions for the discovery of MLCT chromophores.
INORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Amanda A. Volk, Robert W. Epps, Daniel T. Yonemoto, Benjamin S. Masters, Felix N. Castellano, Kristofer G. Reyes, Milad Abolhasani
Summary: AlphaFlow is a self-driven fluidic lab that enables autonomous discovery and optimization of complex multi-step chemistries through reinforcement learning. It successfully identified and optimized a novel multi-step reaction route that outperformed conventional sequences.
NATURE COMMUNICATIONS
(2023)
Article
Multidisciplinary Sciences
Shahnawaz Rafiq, Nicholas P. Weingartz, Sarah Kromer, Felix N. Castellano, Lin X. Chen
Summary: Design-specific control over the transitions between excited electronic states of different spin multiplicities is crucial. Previous studies have shown that the spin-vibronic effect can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, identifying precise experimental manifestations of this mechanism has been challenging. In this study, coherence spectroscopy experiments reveal the interplay between spin, electronic, and vibrational degrees of freedom in driving efficient singlet-triplet conversion, shedding light on the spin-vibronic mechanism.
Article
Chemistry, Inorganic & Nuclear
Sarah Kromer, Subhangi Roy, James E. Yarnell, Chelsea M. Taliaferro, Felix N. Castellano
Summary: Dinuclear d(8) Pt(ii) complexes exhibit photophysical properties determined by the distance between the two Pt(ii) centres, showing either metal-to-ligand-(MLCT) or metal-metal-ligand-to-ligand charge transfer (MMLCT) transitions. The novel dinuclear complexes with 8-hydroxyquinoline as the bridging ligand possess similar photophysics to the mononuclear model chromophore. TD-DFT calculations confirm the mixed LC/MLCT nature of the lowest energy absorption and the limited quantum yields of the (LC)-L-3 photoluminescence for these complexes.
DALTON TRANSACTIONS
(2023)
Article
Materials Science, Multidisciplinary
Rishabh D. Guha, Evgeny O. Danilov, Katherine Berkowitz, Oluwatimilehin Oluwajire, Landon R. Grace
Summary: Moisture absorption leads to the performance degradation of epoxy-based polymer materials. The state of water molecules in crosslinked epoxy is influenced by the secondary bonding interactions and local physical environment. The curing schedule can be modified to control the chemical and physical variables on a macroscopic scale. This study investigated the correlation between moisture absorption, network morphology, and dielectric properties by curing crosslinked epoxy matrices with different network architectures and subjecting them to fluctuating humidity conditions.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Physical
Fazel Bateni, Sina Sadeghi, Negin Orouji, Jeffrey A. Bennett, Venkat S. Punati, Christine Stark, Junyu Wang, Michael C. Rosko, Ou Chen, Felix N. Castellano, Kristofer G. Reyes, Milad Abolhasani
Summary: This study introduces Smart Dope, a self-driving fluidic lab technology, for accelerated synthesis and autonomous optimization of lead halide perovskite quantum dots. Through the use of a high-pressure gas-liquid segmented flow format, Smart Dope successfully synthesizes multi-cation-doped CsPbCl3 quantum dots and autonomously discovers the optimal synthetic route with a photoluminescence quantum yield of 158%.
ADVANCED ENERGY MATERIALS
(2023)
Article
Multidisciplinary Sciences
Yan Wang, Sina Sadeghi, Alireza Velayati, Rajesh Paul, Zach Hetzler, Evgeny Danilov, Frances S. Ligler, Qingshan Wei
Summary: This article introduces a cost-effective and miniaturized smartphone lifetime imaging system that utilizes a virtual mechanical chopper mechanism and machine learning for 2D luminescence lifetime imaging. The system can measure the luminescence lifetime at each pixel with a relatively low acquisition frame rate and eliminates the need for expensive and complicated instruments used in traditional time-resolved detection.
Article
Chemistry, Inorganic & Nuclear
Dooyoung Kim, Michael C. Rosko, Vinh Q. Dang, Felix N. Castellano, Thomas S. Teets
Summary: One of the main challenges in developing effective copper(I) photosensitizers is their short excited-state lifetimes. In this study, steric modifications were introduced to improve the excited-state lifetimes of these complexes, and the effects of alkyl groups on the excited-state dynamics were investigated. The results revealed that sterically encumbered complexes exhibited significantly longer excited-state lifetimes compared to the unsubstituted complex.
INORGANIC CHEMISTRY
(2023)