Article
Chemistry, Organic
Elvira R. Zaitseva, Victoria E. Opryshko, Dmitrii S. Ivanov, Andrey A. Mikhaylov, Alexander Yu. Smirnov, Mikhail S. Baranov
Summary: In this study, it was found that 2-Allyloxybenzaldehydes readily undergo [2 + 1] cycloadditions under 365 nm LED irradiation to form chroman-fused cyclopropanols. This reaction occurs without the need for any catalysts or additives in dimethyl sulfoxide.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Emily A. Boyd, Jonas C. Peters
Summary: “This study provides a well-defined functional model for the proton-coupled electron transfer (PCET) reactivity of samarium diiodide (SmI2) by using a bulky and strongly chelating macrocyclic ligand. By comparing with similar systems in tetrahydrofuran (THF), the study reveals exceptionally weak N-H and O-H bond dissociation free energy (BDFE) values in 2-pyrrolidone and methanol complexes. The results suggest potential for achieving catalytic turnover using SmII-based PCET reagents.”
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Dengbing Xie, Ming Lin, Pengkai Wang, Lingyu Zhang, Songlin Zhang
Summary: The reduction of cyanoximes to aromatic nitriles via N-centered anions from the reductive cleavage of N-O-ΘΘΘΘΘΘΘΘ bond in cyanoximes promoted by SmI2 is reported for the first time. A mild, safe, and efficient method for the synthesis of aromatic nitriles in a one-pot fashion with excellent yields was developed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chintada Nageswara Rao, Hans-Ulrich Reissig
Summary: A series of (S)-proline-based enantiopure phosphorus triamide derivatives were prepared and evaluated as an alternative to HMPA in samarium diiodide cyclization reactions of N-acylated indole derivatives. While the chiral Lewis base showed fast conversions and high yields in reactions, there is room for improvement in achieving higher enantioselectivities in practical applications.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hidetaka Kuroiwa, Soichiro Suzuki, Kazuhiro Irie, Chihiro Tsukano
Summary: Lancilactone C is a tricyclic triterpenoid that can inhibit the replication of human immunodeficiency virus (HIV) in H9 lymphocytes without cytotoxicity. It has a tricyclic skeleton consisting of trans-dimethyl-bicyclo[4.3.0]nonane and 7-isopropylene-cyclohepta-1,3,5-triene. The latter structure, in which all carbon atoms are sp (2) hybridized, is unique and needs to be synthetically verified.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jade Dussart-Gautheret, Julie Yu, Krithika Ganesh, Gaikwad Rajendra, Fabrice Gallou, Bruce H. Lipshutz
Summary: This study describes the surfactant-enabled asymmetric ATA-catalyzed reductive aminations in water, which enhance the conversion levels and enable 1-pot chemoenzymatic catalysis. The modified conditions involving both biocatalysis and chemocatalysis are environmentally responsible, indicating the potential of using chemistry in water.
Article
Chemistry, Organic
Chintada Nageswara Rao, Hans-Ulrich Reissig
Summary: Samarium(II)-promoted cyclization reactions of N-acylated indolyl sulfinyl imines without electron-withdrawing groups at C-3 yielded tertiary carbinamines in good yield. The use of excess samarium diiodide in the presence of water and lithium bromide resulted in the cleanest reactions and highest yields. Reductive detachment of the sulfur functional group was observed, likely preceding the cyclization step. Enantioselectivity was not observed when enantiopure sulfinyl imines were used. The mechanisms of N-S cleavage, cyclization of the intermediate imines, and the role of additives are discussed. The presented method gives rise to interesting polycyclic indoline derivatives, with a cascade reaction involving an ethoxycarbonyl-substituted side chain providing unique tetracyclic spiro-gamma-lactams.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Jiawei Xu, Pu Yang, Like Deng, Na Shu, Yunlong Shang, Wanjie Zhou, Jianchun Bao, Min Fang, Yong Wu
Summary: The study describes the N-N bond structure of the key intermediate in catalytic ammonia production as containing a N-N double bond, with the presence of two 3c-delocalized bonds. The reduction of nitrogen mainly occurs during the N-N bond cleavage step. Moreover, the thermodynamics of the catalytic cycle, investigated using the DFT method, reveals that the rate-determining step is the reductive formation of the first N-H bond.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Dengbing Xie, Songlin Zhang
Summary: The selective reduction of quinolin-2(1H)-ones using a SmI2/H2O/MeOH system is reported for the first time. The reaction proceeds effectively under mild conditions, giving 3,4-dihydroquinoline-2(1H)-ones in one pot with good to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Emily A. A. Boyd, Jonas C. C. Peters
Summary: Controlling selectivity in N-2 reduction reactions is challenging. In this study, we developed conditions to shift the selectivity from ammonia (NH3) to hydrazine (N2H4) as the main product. By using a strongly reducing but weakly acidic reagent, the selectivity towards N2H4 was increased without sacrificing activity. Mechanistic data suggested that iron hydrazido(2-) species played a crucial role in determining the selectivity. Furthermore, spectroscopic data indicated the involvement of Sm(III) in catalytic efficacy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Yoonsu Park, Sangmin Kim, Lei Tian, Hongyu Zhong, Gregory D. Scholes, Paul J. Chirik
Summary: This study describes the direct photocatalytic synthesis of extremely weak element-hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol(-1). The key to this approach is the bifunctional behavior of the chromophoric iridium hydride photocatalyst, which enables the formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry.
Article
Chemistry, Organic
Pengkai Wang, Songlin Zhang
Summary: The reduction of 2-nitrophenylacetic acids to oxindoles promoted by SmI2 is reported for the first time. This reaction proceeds through N-O bond cleavage and direct condensation with the neighboring carboxyl group, providing a new method for the synthesis of oxindoles in mild neutral conditions.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Organic
Chen Liu, Yan Qi, Yongjun Liu
Summary: Samarium diiodide has been playing a key role in the field of organic synthesis due to its excellent single electron transfer and reduction abilities. In the past five years, research has focused on reactions mediated by samarium reagents, particularly SmI2, involving coupling reactions and organic reduction reactions.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Nicholas G. Boekell, Caroline O. Bartulovich, Sandeepan Maity, Robert A. Flowers
Summary: Highly reducing Sm(II) reductants and protic ligands were used to investigate the relationship between low-valent metal-protic ligand affinity and degree of ligand X-H bond weakening. The SmBr2-NMEA reagent system demonstrated the best combination of metal-ligand affinity and stability against H2 evolution. It successfully reduced challenging substrates and showed potential for the design of PCET reagents with weak X-H bonds.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Ramees Peedika Paramban, Zhifang Guo, Glen B. Deacon, Peter C. Junk
Summary: Treatment of [Sm(DippForm)(2)(thf)(2)] with 1,3,5,7-cyclooctatetraene in toluene under reductive conditions leads to the formation of an inverse sandwich dinuclear complex [Sm-2(DippForm)(4)(COT)] (1). However, in THF, it generates [Sm(DippForm)(COT)(thf)(2)] (2) and [Sm(DippForm)(2)(O-C4H8-DippForm)(thf)] (3). Furthermore, 1 gives 2 and 3 upon treatment with THF.
DALTON TRANSACTIONS
(2023)
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)