Article
Chemistry, Organic
Xiao-Tong Li, Heng-Zhi Tian, Xing-Wen Sun
Summary: Highly enantioselective synthesis of 3,3'-spirooxindole gamma-lactams with three contiguous stereocenters (two quaternary) was achieved using a bifunctional diaminocyclohexane-derived thiourea catalyst in the aza-Michael/Mannich cascade reaction. The desired products were obtained in moderate to good yields, moderate to good diastereoselectivities, and good to excellent enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Fabian Scharinger, Matthias Weil, Michael Schnuerch, Katharina Bica-Schroeder
Summary: We introduce a simple method for the synthesis of chiral diazabicycloalkanes in a single reaction step. This method is applicable to a wide range of enals and has high functional group tolerance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Guanping Tang, Samuel K. Akompong, Lianxun Gao, Chen Zeng, Hengjiang Cong, Mian Yang, Long Ye, Yi Liu
Summary: The Zn(OAc)(2)-mediated Mannich-type reaction shows great potential in the synthesis of 3,3'-pyrrolidinyl-spirooxindole, providing high yields of the target product under optimized conditions. This reaction is influenced by various factors such as metal salt, base, stoichiometry, stereoelectronics, and temperature.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Applied
Fushuai Li, Zhihong Yang, Yanyan Yang, Qiuhong Huang, Xuling Chen, Pengfei Li, Mingxin Dong, Wenjun Li
Summary: A chiral phosphorus acid catalyzed enantioselective 1,4-conjugate addition of arylamines to in situ formed 7-methylene-7H-indoles from 7-indolylmethanols has been successfully developed for the first time without the use of additives. The catalytic protocol enables the formation of 1,4-adducts with a nitrogen-containing tertiary carbon stereocenter in moderate to high yields and good enantioselectivity under mild reaction conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Ruiying Ma, Hongzhou Yang, Ling Ye, Qiang Yang, Zhichuan Shi, Zhigang Zhao, Xuefeng Li
Summary: A one-pot, two-step aza-Michael/Michael/Michael process has been developed for the diastereospecific construction of C6a,C10acis-hydrophenanthridines in a highly enantioselective manner (83-99% ee). The tricyclic products were obtained in 50-99% isolated yields, sequentially promoted by bifunctional squaramide and diamine in a one-pot operation. This doubly annulative protocol demonstrates the facile construction of complex polycyclic structures through the full utilization of available reaction sites in readily prepared precursors.
Article
Chemistry, Organic
Prasenjit Gayen, Prasanta Ghorai
Summary: A highly chemoselective 1,2-addition of thiols with 2-isothiocyanatochalcones followed by an enantioselective intramolecular thia-Michael addition cascade has been developed for the synthesis of enantioenriched [1,3]-benzothiazine derivatives. The squaramide catalyst derived from cinchona provides excellent yield and enantioselectivity with a wide range of substrates. Furthermore, this strategy can be extended to access enantioenriched organophosphorus-substituted [1,3]-benzothazines using diphenylphosphine oxide nucleophile.
Article
Chemistry, Organic
Xi-Xi Wu, Yonghui He, Xiu-Xiu Qiao, Tao Ma, Chang-Peng Zou, Ganpeng Li, Xiao-Jing Zhao
Summary: The study developed a challenging direct organocatalytic asymmetric aza-MBH reaction involving cyclic ketimines attached to a neutral functional group. α,β-unsaturated γ-butyrolactam was used as a rare nucleophile alkene in this reaction. The reactions provided enantiomerically enriched 2-alkenyl-2-phenyl-1,2-dihydro-3H-indol-3-ones with high alpha-selectivities, high enantioselectivities (up to 99% ee), and good yields (up to 80%).
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Pratibha Sharma, Raakhi Gupta, Raj K. Bansal
Summary: The article reviews the literature on asymmetric aza-MR of amines and amides catalyzed by organocatalysts in the past 10 years. Studies show that both types of organocatalysts, whether through non-covalent interactions or through covalent bond formation, play important roles in this reaction.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xiu-Ning Hu, Dong-Ping Wu, Ye-Peng Xu, Pei-Qiang Huang
Summary: The first organocatalytic asymmetric synthesis of an advanced intermediate of (+)-sarain A was achieved by combining organocatalytic asymmetric Michael addition reaction and a nitrogen-to-carbon chirality transfer. This method allows for the construction of three chiral centers and chemoselective reduction of a key lactam intermediate, providing a tricyclic intermediate with all necessary functionalities for further elaboration into (+)-sarain A.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Zhe Chen, Tianyi Zhang, Yuhong Sun, Liming Wang, Ying Jin
Summary: An organocatalytic enantioselective Friedel-Crafts alkylation of beta-naphthols with isatins has been developed, yielding enantioenriched products in high yields and enantioselectivities. This methodology expands the catalyst type and substrate scope.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Leonardo Straminelli, Francesco Vicentini, Antonio Di Sabato, Carmela Maria Montone, Chiara Cavaliere, Kari Rissanen, Francesca Leonelli, Fabrizio Vetica
Summary: A highly stereoselective procedure for the synthesis of spiro-polycyclic oxindoles bearing five contiguous stereogenic centers including two tetrasubstituted carbons has been developed. The sequence involves sequential organocatalysis using a pyrrolidine-based organocatalyst and DBU, resulting in an atom-economical Michael-domino Michael/aldol reaction sequence. The reaction yielded variously functionalized spiro-decalin oxindoles with excellent stereoselectivity (>99:1 dr, up to 92% ee).
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ruslan A. Kovalevsky, Maxim Smirnov, Alexander S. Kucherenko, Kseniya A. Bykova, Elizaveta Shikina, Sergei G. Zlotin
Summary: In this study, 2-nitroallylic carbonates were used for the first time as promising biselectrophilic C3 synthons. They reacted with kojic acid derivatives in a bifunctional squaramide catalyzed asymmetric domino reaction, yielding nitro compounds that contain two hydroxypyranone units. The reaction products undergo noncatalytic epimerization at the carbon atom next to the nitro group. A plausible mechanism of the epimerization based on reversible formation of intermediate aci-nitro compound is proposed. The double addition products were transformed into configurationally stable acetates and chiral nitro glutarates, which are promising precursors for chiral amino glutaric acid derivatives.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ziyang Wang, Xiao Lin, Xuling Chen, Pengfei Li, Wenjun Li
Summary: A chiral phosphoric acid-catalyzed enantioselective 1,6-conjugate addition of thiolacetic acid to alkynyl indole imine methide in situ formed from alpha-(3-indolyl) propargylic alcohol has been developed, enabling the formation of axially chiral sulfur-containing tetrasubstituted allenes in generally high efficiency with stereoselectivity.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Multidisciplinary
Yin Xu, Tong-Yi Zhai, Zhou Xu, Long-Wu Ye
Summary: Desymmetrization is a practical and efficient strategy in synthetic chemistry for assembling valuable molecular complexity. Organocatalysis has become a powerful tool in asymmetric catalysis, and recent progress has been made in combining organocatalysis with desymmetrization.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhi-Hao You, Sheng Zou, Ya-Li Song, Xue-Qing Song
Summary: An organocatalyzed asymmetric synthesis of fused butyrolactones has been established via a one-pot process. The reaction involves the formal [2 + 2 + 2] annulation between gamma-butenolides, methylene indolinones, and nitroolefins. The L tertleucine-derived bifunctional thiourea catalyst provides good yields (up to 95%) and excellent enantioselectivities (up to >99% ee).
Article
Chemistry, Applied
Peng Wu, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: Copper-catalyzed cross-coupling reactions of alpha-bromoaryl NH-sulfoximines with elemental sulfur were used to synthesize benzo[d][1,3,2]dithiazole-1-oxides, which belong to a new class of three-dimensional heterocycles. The reactions exhibited good functional group and heterocycle tolerance under mild conditions. Moreover, the initial cross-coupling products could be converted to unprecedented cyclic sulfonimidamides derivatives through imination/oxidation. Additionally, a seven-membered heterocycle was obtained by a ruthenium-catalyzed ring-expansion with ethyl propiolate.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Christian Schumacher, Jas S. Ward, Kari Rissanen, Carsten Bolm, Mohamed Ramadan El Sayed Aly
Summary: Cholesterol can react under Appel conditions to form 3,5-cholestadiene and 313-bromocholest-5-ene, which deviates from the stereochemistry of the standard Appel mechanism due to the involvement of A5 pi-electrons. However, the subsequent azidolysis of 313-bromocholest-5-ene proceeds mainly by Walden inversion, resulting in the formation of 3a-azidocholest-5-ene. The structures of the products were confirmed by X-ray crystallography and the NMR data matched the reported data.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Arjuna Selvakumar, Mostafa M. Amer, Khai-Nghi Truong, Kari Rissanen, Carsten Bolm
Summary: Copper(I)-catalyzed domino reactions of 2-azido sulfoximines with 1-iodoalkynes afford fused triazolyl-containing benzothiadiazine-1-oxides in one step with high yields. This method exhibits broad functional group tolerance and allows the synthesis of two fused heterocyclic rings. Mechanistic investigations reveal the involvement of a copper pi-complex and an iodinated triazole intermediate in the reaction sequence.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Ettore Bartalucci, Christian Schumacher, Leeroy Hendrickx, Francesco Puccetti, Igor d'Anciaes Almeida Silva, Riza Dervisoglu, Rakesh Puttreddy, Carsten Bolm, Thomas Wiegand
Summary: Mechanical forces, including compressive stresses, have a significant impact on chemical reactions. The absence of organic solvents, synthetic acceleration, and unique reaction pathways make mechanochemical conditions advantageous. An accurate characterization of ball-milling products and a deeper mechanistic understanding of the transformations at a molecular level are critical for fully realizing the potential of organic mechanosynthesis.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jas S. Ward, Elina I. Sievanen, Kari Rissanen
Summary: Solid-state NMR was used to study a series of Barluenga-type iodine(I) [L-I-L]PF6 complexes (L=pyridine, 4-ethylpyridine, 4-dimethylaminopyridine, isoquinoline) and their respective non-liquid ligands (L), precursor silver(I) complexes, and N-methylated pyridinium and quinolinium hexafluorophoshate salts. The results were compared to solution studies and single-crystal X-ray structures. Practical considerations were discussed to encourage wider utilization of this technique in the future as the first study of its kind on the solid-state NMR behavior of halogen(I) complexes.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Kwaku Twum, Sanaz Nadimi, Frank Boateng Osei, Rakesh Puttreddy, Yvonne Bessem Ojong, John J. Hayward, Kari Rissanen, John F. Trant, Ngong Kodiah Beyeh
Summary: In this study, the formation of a three-component halogen-bonded ternary assembly in a protic polar solvent system is achieved by utilizing the binding of fused aromatic N-heterocycles in an open resorcinarene cavity to template the assembly. This approach overcomes the challenges posed by the overwhelming quantity of competing solvent.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Laura M. E. Wilson, Kari Rissanen, Jas S. Ward
Summary: A series of iodine(i) complexes, both known and new, were synthesized to investigate the influence of Lewis bases and anions on iodination reactivity. The iodination capability of the iodine(i) species was tested and compared using a screening protocol based on the iodination of antipyrine. The results showed that both the identity of Lewis bases and anions affect the iodination capability, and less efficient reagents can still deliver comparable percentage conversions with longer reaction times.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Guillermo Romo-Islas, Jas S. Ward, Kari Rissanen, Laura Rodriguez
Summary: The use of heterometallic Au/Cu systems with metallophilic contacts is ideal for obtaining red phosphorescent materials. The synthesized compounds have an ionic character due to the reaction of gold-(I) complexes with copper-(I) salts, and the counterion affects the emission wavelength. These compounds have been tested as photosensitizers for generating singlet oxygen.
INORGANIC CHEMISTRY
(2023)
Article
Plant Sciences
Emanuel T. Mahambo, Colores Uwamariya, Masum Miah, Leandro da Costa Clementino, Luis Carlos Salazar Alvarez, Gabriela Paula Di Santo Meztler, Edward Trybala, Joanna Said, Lianne H. E. Wieske, Jas S. Ward, Kari Rissanen, Joan J. E. Munissi, Fabio T. M. Costa, Per Sunnerhagen, Tomas Bergstrom, Stephen S. Nyandoro, Mate Erdelyi
Summary: Six new crotofolane diterpenoids (1-6) and 13 known compounds (7-19) were isolated from Croton kilwae. The structures of the new compounds were determined by analyzing spectroscopic and mass spectrometric data. Some of the compounds exhibited antiviral, antibacterial, and antimalarial activities.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Chemistry, Multidisciplinary
Kari Rissanen, Jas S. Ward
Summary: This study synthesized new iodine(I) complexes using silver(I) complexes and explored the influence of different functional substituents. The properties of these rare iodine(I) complexes containing 3-substituted pyridines were compared to their more prevalent 4-substituted counterparts.
Article
Chemistry, Organic
Christina Jager, Martin Nieger, Kari Rissanen, Jan Deska
Summary: A triple-enzymatic strategy is developed for the direct conversion of γ,δ-unsaturated esters to N-hydroxy-γ-lactam building blocks. This methodology provides a mild and scalable access to N-heterocyclic building blocks and is successfully employed in the synthesis of key intermediates en route to alkaloids of the Cephalotaxus family.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Teresa M. Karl, Samir Bouayad-Gervais, Julian A. Hueffel, Theresa Sperger, Sebastian Wellig, Sherif J. Kaldas, Uladzislava Dabranskaya, Jas S. Ward, Kari Rissanen, Graham J. Tizzard, Franziska Schoenebeck
Summary: Due to the unknown correlation between a metal's ligand and its resulting preferred speciation in terms of oxidation state, geometry, and nuclearity, the rational design of multinuclear catalysts is still challenging. In this study, we employed an assumption-based machine learning approach to accelerate the identification of suitable ligands for trialkylphosphine-derived dihalogen-bridged Ni-(I) dimers. We experimentally verified the predictions, synthesized novel Ni-(I) dimers, and explored their potential in catalysis, achieving C-I selective arylations of polyhalogenated arenes with competing C-Br and C-Cl sites in under 5 min at room temperature using the newly developed dimer, [Ni-(I)(& mu;-Br)PAd(2)(n-Bu)](2), which has not been met with alternative dinuclear or mononuclear Ni or Pd catalysts so far.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yiwei Gong, Jas S. Ward, Kari Rissanen, Florian F. Mulks
Summary: Site-selective functionalization of pyridines is crucial for the synthesis of pharmaceuticals and materials. We introduce diiminium pyridine adducts as convenient and potent Lewis acids, and report the selective addition of tributylphosphine to the 4-position of pyridine. This finding advances the utilization of diiminium units as organic reagents or catalysts for pyridine functionalization. Computational models provide valuable insights for future investigations in this area.
Article
Chemistry, Multidisciplinary
Rene Hommelsheim, Sandra Bausch, Robin van Nahl, Jas S. Ward, Kari Rissanen, Carsten Bolm
Summary: A variety of 3-amino-substituted benzothiadiazine oxides were synthesized via a one-step palladium-catalyzed cascade reaction of 2-azido sulfoximines with isonitriles. The desired heterocycles were obtained in good to excellent yields using very low catalyst loadings and short reaction times. This protocol provides direct access to precursors for pharmaceutically relevant sulfoximines.
Article
Chemistry, Multidisciplinary
Milla Mattila, Kari Rissanen, Jas S. Ward
Summary: Three chiral carbonyl hypoiodites were synthesized from N-protected (S)-valine and formed ligand-stabilised (S)-valinoyl hypoiodite complexes with 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 4-morpholinopyridine as stabilising ligands. The structures of the complexes were determined through NMR (H-1, C-13, H-1-N-15 HMBC) and single crystal X-ray diffraction analysis.
CHEMICAL COMMUNICATIONS
(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)
