Article
Chemistry, Multidisciplinary
Dipshi Singh, T. V. RajanBabu
Summary: We report two distinctly different, catalyst-dependent, modes of regio- and enantioselective cycloaddition reactions between alkynes and 1,3-dienes providing rapid access to highly functionalized 1,4-cyclohexadienes or cyclobutenes from the same precursors. Complexes of an earth abundant metal, cobalt, with several commercially available chiral bisphosphine ligands with narrow bite angles catalyze [4+2]-cycloadditions with excellent chemo-, regio- and enantioselectivities. In contrast, complex of a finely tuned phosphino-oxazoline ligand promotes unique [2+2]-cycloaddition between the alkyne and the terminal double bond of the diene giving a highly functionalized cyclobutene with excellent regio- and enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Hua Zhao, Yufen Zhao
Summary: Multicomponent reactions (MCRs) have become indispensable tools for organic chemists worldwide, finding extensive utility in the synthesis of complex natural products, heterocyclic molecules with significant bioactivity, and pharmaceutical agents. The multicomponent one-pot 1,3-dipolar cycloaddition reaction is highly favored in terms of green synthesis due to its high step- and atom-economies, remarkable product diversity, as well as excellent efficiency and diastereoselectivity.
Review
Chemistry, Organic
Joaquin Plumet
Summary: The 1,3-dipolar cycloadditions of nitrile oxides have been widely used in synthetic organic chemistry as a powerful tool. The cycloadducts arising from the cycloadditions of nitrile oxides to alkenes and alkynes are valuable synthetic intermediates due to their capacity to mask other functionalities, with the beta-hydroxy ketone functionality being an illustrative example.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yuvraj Garg, James Osborne, Serhii Vasylevskyi, Nivedha Velmurugan, Fujie Tanaka
Summary: 1,3-Diamine-derived catalysts were synthesized and utilized in asymmetric Mannich reactions of ketones. The Mannich products with high enantioselectivities were obtained under mild conditions through catalysis by one of the 1,3-diamine derivatives in the presence of acids. Bond formation primarily occurred at the less-substituted α-position of the ketone carbonyl group. The primary and tertiary amines of the 1,3-diamine derivative cooperatively acted for the catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Nikita A. Kaminskiy, Ekaterina E. Galenko, Mariya A. Kryukova, Mikhail S. Novikov, Alexander F. Khlebnikov
Summary: This study discovered that alpha-diazopyrroles selectively react with enamines at room temperature to produce organic compounds, which can be used for the synthesis of functionalized heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yi-Sen Qian, Zi-Lu Wang, Bing Jiang, Zhen-Yu Xiao, Yun-He Xu
Summary: This study reports the copper-catalyzed borylation and silylation of dichlorocyclobutenones, leading to the synthesis of boron-substituted and silicon-substituted polyfunctionalized cyclobutenones with high yields. The reactions occur under mild conditions, exhibit broad substrate scope, and show high chemoselectivity. Furthermore, a series of transformations of the resulting products have been achieved.
Article
Chemistry, Organic
Arthur Lebrene, Thomas Martzel, Laura Gouriou, Morgane Sanselme, Vincent Levacher, Sylvain Oudeyer, Carlos Afonso, Corinne Loutelier-Bourhis, Jean-Francois Briere
Summary: A straightforward method for synthesizing original 1,6-diazabicyclo[4.3.0]nonane-2,7-diones was developed using a DBU-organocatalyzed multicomponent Knoevenagel-aza-Michael-Cyclocondensation reaction. Analysis of key reactive intermediates using mass spectrometry confirmed the proposed mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kan-Lei Ji, Shu-Fan He, Dong-Dong Xu, Wen-Xin He, Jian-Feng Zheng, Pei-Qiang Huang
Summary: A concise asymmetric total synthesis of (-)-quinocarcin has been achieved through high step economy using commercially available starting materials. The key chiral pyrrolidine intermediate with three stereocenters was prepared via a catalytic enantioselective reductive 1,3-dipolar cycloaddition reaction. This synthesis also involved a Rh-III-catalyzed C-H activation/cyclization and a tandem diastereoselective hydrogenation/cyclization to construct the tetrahydroisoquinoline-pyrrolidine tetracyclic core unit of quinocarcin.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jackson S. Henneveld, Farshad Shiri, Alireza Ariafard, Nigel T. Lucas, Alex C. Bissember, Bill C. Hawkins
Summary: The investigation and formalization of the distinctive dipole-transmissive dipolar cycloaddition (DTDC) methodology is reported. A DTDC procedure was developed by taking advantage of the structural complementarity of azide and diazoalkane 1,3-dipoles. This method allows for the rapid construction of functionalized polycyclic N-heterocycles through intramolecular azide-alkene 1,3-dipolar cycloadditions followed by N-derivatization and subsequent 1,3-dipolar cycloadditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wang Yao, Chuan-Jun Lu, Li-Wen Zhan, Yi Wu, Jia Feng, Ren-Rong Liu
Summary: In this study, a palladium-catalyzed enantioselective C-H activation method for pyrroles was reported, which successfully synthesized structurally diverse indole-pyrrole atropisomers with a chiral N-N axis, showing high yields and enantioselectivities. Furthermore, the kinetic resolution of trisubstituted N-N heterobiaryls with more sterically demanding substituents was also achieved. This versatile method enables the rapid and selective functionalization of pyrroles, facilitating the synthesis of valuable and complex N-N atropisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Applied
Daniel Gavina, Marcos Escolano, Javier Torres, Gloria Alzuet-Pina, Maria Sanchez-Rosello, Carlos del Pozo
Summary: Substituted and annulated pyrroles containing chiral centers can be accessed through organocatalytic enantioselective Friedel-Crafts alkylation (FCA) reaction. These compounds are interesting due to their natural occurrence and diverse biological activities. In the past two decades, significant synthetic efforts have been made to develop asymmetric transformations involving pyrroles in the FCA reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Skyler D. Mendoza, Michael Rombola, Yujia Tao, Stephan J. Zuend, Roland Goetz, Martin J. McLaughlin, Sarah E. Reisman
Summary: An enantioselective Diels-Alder reaction using yttrium triflate as catalyst has been developed for the synthesis of chiral oxidized cyclohexenes. This method allows the preparation of a key intermediate in the synthesis of commercial herbicide cinmethylin.
Article
Multidisciplinary Sciences
Bing-Bing Sun, Kun Liu, Quan Gao, Wei Fang, Shuang Lu, Chun-Ru Wang, Chuan-Zhi Yao, Hai-Qun Cao, Jie Yu
Summary: This article reports on a strategy that enables enantioselective Ugi four-component and Ugi-azide reactions using anionic stereogenic-at-cobalt(III) complexes as catalysts. By controlling the generation and trapping of key nitrilium intermediates, highly enantioselective alpha-acylamino amides and alpha-aminotetrazoles can be obtained.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Xiang Cheng, Xin Chang, Yuhong Yang, Zongpeng Zhang, Jing Li, Yipu Li, Wenxiao Zhao, Lung Wa Chung, Huailong Teng, Xiu-Qin Dong, Chun-Jiang Wang
Summary: A copper-catalyzed asymmetric 1,3-dipolar cycloaddition method was developed for the synthesis of enantioenriched pyrrolidines with trifluoromethyl group. The reaction shows good to high yields and excellent levels of stereo- and regioselectivity. In addition, a substrate-controlled umpolung-type dipolar cycloaddition reaction was also discovered. DFT studies suggest that the observed high stereo- and regioselectivity may be attributed to the in-situ reduction of copper(II) salt to active copper(I) species.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Francisco V. Gaspar, Marcelo F. M. F. Azevedo, Leonardo S. A. Carneiro, Samuel B. Ribeiro, Pierre M. Esteves, Camilla D. Buarque
Summary: This study reports the synthesis of new 4-acyl-1,2,3-triazoles through metal-free and solvent-free cycloaddition reactions, achieving high yields. The reaction mechanism for the synthesis of 4-acyl-1,2,3-triazoles was proposed based on experimental and theoretical data.
