Article
Chemistry, Organic
Ikuya Fujii, Kazuhiko Semba, Yoshiaki Nakao
Summary: Rhodium-aluminum bimetallic complexes catalyze the Kumada-Tamao-Corriu (KTC) cross-coupling reaction using arylmagnesium compounds generated from corresponding aryl fluorides or chlorides. This method allows the challenging KTC coupling reaction to be carried out using aryl fluorides as nucleophiles, resulting in various biaryls.
Article
Chemistry, Organic
Quentin D. Tercenio, Erik J. Alexanian
Summary: The nickel-catalyzed reductive coupling of allyl alcohols with chiral, nonracemic alkyl tosylates reported in this study delivers valuable allylation products with high levels of stereospecificity across a range of substrates. The catalytic system, consisting of a simple nickel salt and a commercially available reductant, represents a rare example of a cross-coupling involving the C-O bonds of two electrophiles.
Article
Chemistry, Multidisciplinary
Giuseppe Dilauro, Francesco Messa, Fabio Bona, Serena Perrone, Antonio Salomone
Summary: A simple cobalt complex, Co(phen)Cl₂, has been found to be a highly efficient and cost-effective precatalyst for various cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl, and alkyl bromides. New C(sp²)-C(sp²) and C(sp²)-C(sp³) bonds can be formed in good to excellent yields and high chemoselectivity under mild reaction conditions.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ruofei Cheng, Graham de Ruiter, Chao-Jun Li
Summary: Cobalt-based catalysts have shown unique advantages in cross-coupling reactions, with higher catalytic activity and lower toxicity compared to palladium and nickel catalysts. A novel cobalt-catalyzed alkyl-alkyl cross-coupling reaction of hydrazone with alkyl halides has been developed under mild reaction conditions, using a PNP-type pincer ligand as an essential catalyst. Both aldehyde and ketone hydrazones are compatible with this reaction, producing a series of C(sp(3))-C(sp(3)) coupling products in moderate to good yields.
CHEMICAL COMMUNICATIONS
(2022)
Letter
Chemistry, Organic
Panchi Guo, Hao Jin, Jinhui Han, Liang Xu, Pengfei Li, Miao Zhan
Summary: This study demonstrates a nickel-catalyzed Negishi cross-coupling reaction for the synthesis of versatile organoboron products with high functional-group tolerance. The reaction allows for the coupling of unactivated tertiary alkyl electrophiles with boron-stabilized organozinc reagents. The importance of the Bpin group in accessing the quaternary carbon center is highlighted, and the practicality of the prepared quaternary organoboronates is showcased through their conversion to other useful compounds.
Article
Chemistry, Organic
Bryan C. Figula, D. Lucas Kane, Kaluvu Balaraman, Christian Wolf
Summary: Cross-coupling of alkyl fluorides and organocuprates is achieved via aluminum halide mediated C-F bond activation, leading to the formation of Csp2-Csp3 and Csp3-Csp3 bonds. The reaction exhibits mild conditions and effectively controls competing side reactions, resulting in high yields and good functional group tolerance.
Article
Chemistry, Organic
Kaluvu Balaraman, Christian Wolf
Summary: The Suzuki cross-coupling of benzylic and unactivated aliphatic fluorides with aryl- and alkenylboronic acids has been successfully achieved through mechanistically distinct Pd and Ni catalyzed pathways, demonstrating superiority over competing reactions in over 20 examples. The potential utility of this method is showcased in various compounds, including heterocyclic structures, 1,1-disubstituted and trans-1,2-disubstituted alkenes.
Article
Chemistry, Multidisciplinary
Nikki J. Bakas, Pablo Chourreu, Eric Gayon, Guillaume Lefevre, Michael L. Neidig
Summary: The molecular-level role of alkoxide salts as alternative additives in iron-catalyzed cross-coupling reactions is investigated. Spectroscopic studies reveal that alkoxides promote the formation of homoleptic organoferrates, providing a non-toxic alternative to N-methylpyrrolidone for accessing reactive intermediates.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jiabao Wang, Yuxin Gong, Deli Sun, Hegui Gong
Summary: A Ni-catalyzed reductive cross-coupling reaction has been developed for the construction of benzylated all-carbon quaternary centers. The reaction yields moderate to excellent results with high functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Multidisciplinary Sciences
Eiji Shirakawa, Yuki Ota, Kyohei Yonekura, Keisho Okura, Sahiro Mizusawa, Sujan Kumar Sarkar, Manabu Abe
Summary: An electron has been found to catalyze the cross-coupling reaction of organometallic compounds with aryl halides, which is more desirable for green and sustainable chemistry compared to transition metal catalysis. However, high temperature is required for this electron catalysis. We discovered that visible light photoirradiation can accelerate the electron-catalyzed reaction by using photoredox catalysis, enabling the reaction to proceed at room temperature. The supply of the electron catalyst through photoredox catalysis also expands the scope of aryl halides.
Article
Chemistry, Organic
Quan Lin, Hegui Gong, Fan Wu
Summary: Here, we present a nickel-catalyzed reductive coupling reaction of bromopyridines with tertiary alkyl bromides, enabling the synthesis of alkylated pyridines bearing an all-carbon quaternary center. This strategy offers mild conditions, a broad substrate scope, and high functional group tolerance. We believe this method provides an alternative solution to the challenging task of synthesizing sterically congested alkylpyridines, benefiting the synthetic community and pharmaceutical industry.
Article
Chemistry, Organic
Cassandra R. Youshaw, Ming-Hsiu Yang, Achyut Ranjan Gogoi, Angel Renteria-Gomez, Lei Liu, Lukas M. Morehead, Osvaldo Gutierrez
Summary: In this study, a method for achieving enantioselectivity in carbon-carbon cross-coupling reactions using iron-based catalysts is reported. By using chiral bisphosphine ligands, multicomponent cross-coupling reactions of vinyl boronates, (fluoro)-alkyl halides, and Grignard reagents can be achieved with up to 91:9 enantioselectivity, using commercially available and expensive iron salts.
Article
Chemistry, Multidisciplinary
Hao Liang, James P. Morken
Summary: Enantioenriched tertiary alkylboronic esters can be activated by in situ generated adamantyllithium, leading to stereoretentive boron-to-copper transmetalation. The resulting alkylcopper species can react with various electrophiles through cross-coupling reactions, providing synthetically useful compounds with quaternary stereocenters. DFT calculations of the transmetalation process offer insights into reactivity and selectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Jack A. Killion, William T. Darrow, Marshall R. Brennan, Clare A. Leahy, Alison R. Fout
Summary: A highly efficient catalyst was developed for the Kumada coupling of aryl Grignard reagents to sterically encumbered alkyl halides. The catalyst showed excellent substrate scope and functional group tolerance.
Article
Chemistry, Organic
Yunfei Sha, Jiandong Liu, Liang Wang, Demin Liang, Da Wu, Hegui Gong
Summary: This study presents a facile method for constructing 1,3-dienes by cross-electrophile coupling of two open-chain vinyl halides, with moderate chemoselectivities observed between terminal bromoalkenes and internal vinyl bromides. The mild method is tolerant of various functional groups and can be applied to the total synthesis of solanone, a tobacco fragrance compound.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Afzal Siddiqui, Sachin Thawarkar, Surya Prakash Singh
Summary: A novel perylene diimide derivative was synthesized and investigated to examine the effect of bulky group on the formation of nano-architectonics. Experimental techniques revealed the mechanism and properties of the highly ordered nano and microstructures. The study also explored the impact of substituents on the morphology and absorption properties of the compound through DFT calculations.
JOURNAL OF SOLID STATE CHEMISTRY
(2022)
Article
Chemistry, Organic
Susumu Tsuda, Kaoru Asahi, Ryota Takahashi, Hiroki Yamauchi, Ryoji Ueda, Takanori Iwasaki, Shin-ichi Fujiwara, Nobuaki Kambe
Summary: Transition-metal catalysts offer new opportunities for challenging carbon-carbon bond-forming reactions compared to native enzymes. In this study, bio-inspired self-inclusion strategy using gamma-cyclodextrin-imidazolium salts led to highly enantioselective and reactive arylations of aldehydes with rhodium catalysts, showcasing excellent yields and high enantiomeric excesses of up to 96%. This approach presents a promising pathway for the development of enantioselective and reactive transition-metal catalysts for asymmetric carbon-carbon bond formation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Babar Suraj Shivaji, Rajamouli Boddula, Akinori Saeki, Surya Prakash Singh
Summary: A novel phenothiazine and perylene diimide-fused [7]helicene SPS-PY-PT with effective aggregation-induced emission (AIE) properties was synthesized, providing a direction for AIE-based sensors.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Devulapally Koteshwar, Seelam Prasanthkumar, Surya Prakash Singh, Towhid H. Chowdhury, Idriss Bedja, Ashraful Islam, Lingamallu Giribabu
Summary: A series of newly designed porphyrin sensitizers were studied for their photovoltaic performance, with those containing the cyanoacrylic acid anchoring group showing higher efficiency. Compared to LG18, sensitizers LG24 and LG26 with conjugated electron acceptors have advantages in terms of spectra and electronic structure.
MATERIALS CHEMISTRY FRONTIERS
(2022)
Article
Nanoscience & Nanotechnology
Bommaramoni Yadagiri, Kamatham Narayanaswamy, Ganesh D. Sharma, Surya Prakash Singh
Summary: We report the design and study of a novel medium bandgap nonfullerene small molecule acceptor NFSMA SPS-TDPP-2CNRh. The incorporation of dicyanomethylene-3hexylrhodanine and furan improves light absorption and electrochemical properties, which is expected to enhance the efficiency of organic solar cells (OSCs).
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Takanori Iwasaki, Wataru Ishiga, Shrinwantu Pal, Kyoko Nozaki, Nobuaki Kambe
Summary: This study presents a mechanistic investigation of the Rh-catalyzed cross-coupling reaction between vinylic ethers and aryl Grignard reagents. Kinetic studies reveal first-order and zeroth-order kinetics with respect to the vinyl ether and aryl Grignard reagents, respectively. Computational studies suggest that the reaction proceeds through Mg cation-assisted insertion/anti-beta-oxygen elimination. The results demonstrate the unique chemoselectivity of the Rh-catalyzed reaction.
Article
Polymer Science
Haruki Nagae, Shin-ya Akebi, Saki Matsushiro, Kazutaka Sakamoto, Takanori Iwasaki, Kyoko Nozaki, Kazushi Mashima
Summary: Active methylene compounds, such as nitrile compounds and carbonyl compounds, can act as chain transfer agents in the alternating copolymerization of CO2 and cyclohexene oxide to produce end-functionalized polycarbonates with narrow molecular weight distribution and high carbonate linkage. Acidic nitrile compounds can also result in double chain propagation to form telechelic polycarbonate diols.
Article
Chemistry, Multidisciplinary
V. Murugesh, Patlolla Ravinder Reddy, Surya Prakash Singh
Summary: A photocatalyst-free, visible-light promoted method for direct conversion of C(sp(2))-H to C(sp(2))-N is presented in this study. Multipurpose benzothiadiazoles are employed as model synthons and secondary amines as aminating agents. Mechanistic study reveals that the radical reaction proceeds through nitrogen-centered radical generation, followed by addition of arenes, enabling an economically efficient amination protocol for benzothiadiazole with secondary amines.
CHEMICAL COMMUNICATIONS
(2023)
Article
Materials Science, Multidisciplinary
Ravulakollu Srinivasa Rao, G. Hanumantha Rao, Ganesh D. Sharma, Surya Prakash Singh
Summary: This paper presents the application of squaraine-fullerene conjugate in single-component organic solar cell devices, achieving a high power conversion efficiency by solvent vapor annealing of the active layer.
Review
Chemistry, Multidisciplinary
Takanori Iwasaki, Nobuaki Kambe
Summary: Carbon-fluorine bonds are stable but can be selectively transformed under appropriate conditions, making them useful synthetic methods in organic chemistry. This review focuses on C-C bond formation at monofluorinated sp(3)-hybridized carbons via C-F bond cleavage, including cross-coupling and multi-component coupling reactions. The mechanisms of C-F bond cleavage on sp(3)-hybridized carbon centers are categorized into three types: Lewis acids promoted F atom elimination, nucleophilic substitution with metal or carbon nucleophiles, and cleavage of C-F bonds via single electron transfer. Furthermore, the unique characteristics of alkyl fluorides compared to other (pseudo)halides as electrophilic coupling counterparts are discussed.
Article
Chemistry, Multidisciplinary
Priksha Rana, Ganesh Udari, Balasubramanian Sridhar, Surya Prakash Singh
Summary: In this study, fullerene (C-70) is demonstrated to be an efficient photoredox catalyst for the synthesis of highly functionalized pyrrolo[2,1-a]isoquinoline compounds. C-70 exhibits excellent light harvesting capability, long triplet state lifetime, photostability, and singlet oxygen generation potential, making it an effective catalyst. Through energy transfer and single electron transfer mechanisms, C-70 promotes the formation of singlet oxygen and superoxide radicals, which further facilitate the synthesis of pyrrolo[2,1-a]isoquinolines through a tandem oxidation-deprotonation and [3+2]-cycloaddition reaction sequence. The protocol allows for the activation of various substrates, leading to the construction of a diverse library of well-decorated pyrrolo[2,1-a]isoquinolines with good functional group tolerance.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
P. Nagarjuna, Vinay Gupta, Anirban Bagui, Surya Prakash Singh
Summary: Two molecularly engineered fullerene-based electron acceptors, BITh-C60 and BITh-C70, were synthesized and characterized. BITh-C70 showed stronger absorption and higher power conversion efficiency (PCE) compared to BITh-C60. The BHJ solar cell based on PffBT4T-2OD:BITh-C70 exhibited a flat EQE spectra of 75% from 380 to 700 nm.
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Takanori Iwasaki, Kazuki Tsuge, Naoki Naito, Kyoko Nozaki
Summary: This study reports an Ir catalyst for the selective hydrogenolysis of urea derivatives, achieving the transformation of less reactive carbonyl compounds in the presence of more reactive ones. The proposed catalyst showed tolerance to highly reactive carbonyl groups such as ester, amide, and carbamate, and exhibited high chemoselectivity towards urea. This research provides a new strategy for the chemical recycling of polyurea resins.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Takanori Iwasaki, Wataru Ishiga, Shrinwantu Pal, Kyoko Nozaki, Nobuaki Kambe
Summary: This study reports the mechanistic investigation of the Rh-catalyzed cross-coupling reaction between vinylic ethers and aryl Grignard reagents. The presence of olefinic ligands significantly affects the catalytic activity of Rh precatalysts. Computational studies reveal that the reaction proceeds through Mg cation-assisted insertion/anti-beta-oxygen elimination, with the Mg countercation coordinating to the ethereal oxygen atom in the transition state.
Article
Chemistry, Physical
Babar Suraj Shivaji, Rajamouli Boddula, Surya Prakash Singh
Summary: The study showcases the aggregation-induced emission (AIE) and mechanofluorochromic (MFC) behavior of BTBT molecules, with the design and synthesis of two new BTBT derivatives. The results reveal the AIE feature of BTBT-TPE and the aggregation-caused quenching (ACQ) effect of BTBT-NMe, providing insights into their potential applications in optoelectronic devices. The theoretical calculations and experimental outcomes support the findings on the electronic distribution and energy investigation, highlighting the importance of mechanical stimuli and aggregation response in these compounds for further investigation.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
