Article
Chemistry, Organic
Jun-Bin Tang, Jun-Qian Bian, Yu-Shuai Zhang, Yong-Feng Cheng, Han-Tao Wen, Zhang-Long Yu, Zhong-Liang Li, Qiang-Shuai Gu, Guo-Qiang Chen, Xin-Yuan Liu
Summary: A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes has been established, providing facile access to various stereo-defined trisubstituted alkenes in high yield under mild reaction conditions.
Article
Chemistry, Organic
Jean Michalland, Samir Z. Zard
Summary: A modular, stereoselective route to trisubstituted (Z)-alkenyl (MIDA)boronates was achieved by preparing vinyl boronate precursors through copper-catalyzed protoboration of propargyl alcohols, followed by radical addition-fragmentation of dithiocarbonates. This approach allowed for highly stereoselective fragmentation with the assistance of the bulky (MIDA)boronate.
Article
Chemistry, Organic
Lucas Segura, Itai Massad, Masamichi Ogasawara, Ilan Marek
Summary: The study introduces an efficient method for preparing synthetically valuable trisubstituted alkenylboronate esters through alkene isomerization of their readily available 1,1-disubstituted regioisomeric counterparts. Both stereoisomers of the target alkenylboronate motif can be selectively obtained from the same starting material using different isomerization catalysts.
Article
Chemistry, Organic
Muyang Yang, Wen Shao, Lin Zuo, Jiajia Wang, Yongzhuo Xu, Guojiang Mao, Guo-Jun Deng
Summary: A metal-free, highly site-selective trifluoromethylaminoxylation of activated and unactivated olefins was developed, allowing direct access to diverse β-trifluoromethyl trisubstituted hydroxylamines, tertiary alcohols, isoxazolines, isoxazolidines, and amino alcohols. The reaction proceeds through a SET process between hydroxylamine and a hypervalent iodine-CF3 reagent, generating two free radicals for regio- and diastereoselective addition to alkenes. The synthetic potential of the method was demonstrated through the late-stage functionalization of the products and various postreaction modifications.
Article
Chemistry, Multidisciplinary
Nicolas Muller, Benedikt S. Schreib, Sebastian U. Leutenegger, Erick M. Carreira
Summary: In this study, the palladium-catalyzed aminoalkynylation of electronically unbiased olefins with iodoalkynes was reported. Using the picolinamide auxiliary, the syn-selective aminoalkynylation of mono-, di-, and trisubstituted alkenes was achieved, leading to the formation of corresponding pyrrolidines in high yield and single diastereomers. The picolinamide also allowed for the rapid synthesis of functionalized olefins and subsequent Pictet-Spengler reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Maxim D. Gotsko, Ivan Saliy, Lyubov' N. Sobenina, Igor A. Ushakov, Boris A. Trofimov
Summary: 1-Tosyl-4-pyrrolyl-1,3-enynes have been synthesized in 37-68% yields via a chemo selective reaction assisted by t-BuOK, using 2-(acylethynyl)pyrroles and tosylmethylisocyanide (TosMIC) as the starting materials, demonstrating a new functionality of TosMIC.
NEW JOURNAL OF CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Meng-Yao Li, Shuyang Zhai, Xiao-Mei Nong, Ao Gu, Jiatong Li, Guo-Qiang Lin, Yingbin Liu
Summary: In recent years, the synthesis and application of alkenes, particularly triphenylethenes (TriPEs), have gained attention due to their lower molecular torsion and balanced conjugation, resulting in the aggregation-induced emission (AIE) effect. The geometry of double bonds significantly affects luminescence, making it important to provide a comprehensive summary of stereoselective synthetic strategies for trisubstituted alkenes. This review outlines common strategies for stereoselective synthesis, discussing the origin of stereoselectivity and the types of substrates, while also exploring the AIE properties of TriPE and its versatile applications in optoelectronic devices, stimuli-responsive materials, sensors, and therapies.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Stefan Weber, Daniel Zobernig, Berthold Stoeger, Luis F. Veiros, Karl Kirchner
Summary: The Mn-catalyzed hydroboration of terminal alkenes and the 1,2-diboration of terminal alkynes with pinacolborane have been successfully achieved. The most active pre-catalyst is a bench-stable alkyl bisphosphine Mn-I complex. The catalytic process involves migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate, which further undergoes B-H bond cleavage or C-H bond cleavage for alkenes and alkynes, respectively, forming active Mn-I boryl and acetylide catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Swetha Jos, Christine Tan, Pierre Thilmany, Alaa Saadane, Carla Slebodnick, Gwilherm Evano, Webster L. Santos
Summary: We have reported a tri-n-butyl phosphine catalyzed hydroboration reaction of ynamides, which provides regio- and stereo-selective formation of (Z)-beta-borylenamides in good yields. Surprisingly, a formal cis addition to the triple bond was observed, and this finding was confirmed by NMR and X-ray crystallography. P-31 NMR studies suggest that a zwitterionic vinylphosphonium intermediate plays a key role in the reaction mechanism. Furthermore, the resulting products were successfully transformed into beta-CF3 enamides via stereoretentive trifluoromethylation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shang-Shi Zhang, Yi-Chuan Zheng, Zi-Wu Zhang, Shao-Yong Chen, Hui Xie, Bing Shu, Jia-Lin Song, Yan-Zhi Liu, Yao-Fu Zeng, Luyong Zhang
Summary: A novel rhodium(III)-catalyzed C-H allylation reaction has been developed using 2-methylidenetrimethylene carbonate as an efficient allylic source, resulting in the synthesis of various branched allylarenes bearing an allylic hydroxyl group in moderate to excellent yields. Five different directing groups, including oxime, N-nitroso, purine, pyridine, and pyrimidine, were found to be compatible in this reaction.
Article
Chemistry, Organic
Rowan I. L. Meador, Robert E. Anderson, John D. Chisholm
Summary: Tertiary benzylic alcohols can react with oxoammonium salts in a tandem elimination/allylic oxidation reaction to synthesize allylic ethers in one step, which can then be cleaved under reductive conditions to yield allylic alcohols.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shreemoyee Kumar, Akshay M. Nair, Chandra M. R. Volla
Summary: This study reported the Ru(ii)-catalyzed C(sp(2))-H arylation of N-tosylbenzamides to access multi-substituted allenylamides, which were further converted to isoquinolone derivatives via base mediated annulation. The protocol features low catalyst loading, mild reaction conditions, high functional group compatibility, and scalability. The unique functionality of the produced allenes allowed for further transformations, expanding the practicality of the protocol.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Nilanjana Mukherjee, Tanmay Chatterjee
Summary: This study discloses a metal-free, iodine-catalyzed oxidative C-H sulfenylation and selenation of alkenes in water, which provides a cost-effective, highly atom-economical, and sustainable synthesis method for valuable vinyl sulfides and selenides, including some aggregation-induced-emission (AIE) active molecules. The method shows several advantages, such as the use of inexpensive reagents, water as the reaction medium, high reaction efficiency, and excellent green chemistry metrics.
Article
Chemistry, Multidisciplinary
Han-Ying Liu, Samuel E. Neale, Michael S. Hill, Mary F. Mahon, Claire L. McMullin
Summary: The copper(i) alumanyl derivative reacts with up to three equivalents of various terminal alkynes, resulting in the sequential formation of cuprous (hydrido)(alkynyl)aluminate, (alkenyl)(alkynyl)aluminate, and bis(alkynyl)aluminate derivatives. The alkene liberation process in the latter step is a unique case of alkyne transfer semi-hydrogenation.
Article
Chemistry, Organic
Suman Dana, Chandan Kumar Giri, Mahiuddin Baidya
Summary: A Ru(II)-catalyzed cross-dehydrogenative Heck-type olefination of arenes with allyl sulfones is reported, utilizing the assistance of weakly coordinating ketone and amide functional groups. This study demonstrates the ambiphilic nature of the allyl sulfone side chain and the absence of beta-sulfonyl elimination in the reaction. Mechanistic studies suggest the involvement of a reversible metalation step, with beta-hydride elimination selectively occurring from the benzylic position.
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)