Article
Chemistry, Organic
Huaxin Zhang, Yongge Xiong, Jiang Bai, Ruchun Yang, Xian-Rong Song, Qiang Xiao
Summary: We introduce a highly efficient and practical method for synthesizing gem-dibromo 1,3-oxazines through 6-endo-dig cyclization of propargylic amides, using N-bromosuccinimide (NBS) as an electrophilic source. This metal-free reaction can be carried out under mild conditions, showing good compatibility with various functional groups and providing excellent yields of the desired products. Mechanistic studies indicate that the reaction proceeds through a double electrophilic attack of NBS on the propargylic amide substrate.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Applied
Quentin Gaignard-Gaillard, Xu Han, Aurelien Alix, Christophe Bour, Regis Guillot, Vincent Gandon, Arnaud Voituriez
Summary: A series of enantioenriched substituted tetrahydropyrrolo[3,2-c]azepine products with axial chirality were synthesized in 63-99% yield through a gold(I)-catalyzed hydroarylation. DFT calculations rationalized the observed reactivity and guided the choice of pyrrole N-substituent to isolate configurationally stable compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Nabakumar Bera, Bhabani Sankar Lenka, Sangita Bishi, Shantanu Samanta, Debayan Sarkar
Summary: A new mechanistic pathway of propargylic alcohol activation by gold(I) catalysis has been proposed, which efficiently synthesizes pyrroles, pyridinones, and indoles. Control experiments confirm the formation of an allene oxide intermediate through the participation of the oxygen atom of propargylic alcohol, and this method is successfully applied to the synthesis of hydroxyalkyl indoles and benzofurans.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Chunming Gui, Yuanyuan Peng, Yang Zhou, Yixuan Zheng, Haifeng Wang, Qiongjiao Yan, Hui Zhou, Wei Wang, Fen-Er Chen
Summary: This paper reports the copper-catalyzed asymmetric propargylic substitution reaction, which efficiently synthesizes multifunctionalized products bearing a terminal alkyne unit with good stereoselectivity. The products can also be easily derivatized into other potentially valuable organic compounds, showing great potential for pharmaceutical development.
Article
Chemistry, Applied
Yao Xiao, Jie Shen, Li Wang, Shanya Lu, Jian Li
Summary: A cascade annulation of 2-isocyanophenyloxyacrylate and propargylic ester under basic conditions has been developed for the diastereoselective synthesis of oxa-bridged tetracyclic benzooxazine. The annulation involves isomerization, Michael addition, triple annulation, and acyl migration processes.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Nikolai P. Rossouw, Zongjia Chen, Jonathan M. White, Mark A. Rizzacasa
Summary: This study reports an approach to achieve higher oxidation of alkyl citrates through direct regio- and stereoselective oxidations. The synthesis and structural assignment of alkyl citrate L-731-128 were described. The C4 oxidized congener L-731,127 was synthesized using regio- and stereoselective enolate oxidation and oxygen gas oxidation. Furthermore, a highly stereoselective Rubottom oxidation was utilized to achieve oxidation at C2, yielding cinatrins C-1 and C-3.
Article
Multidisciplinary Sciences
Yu-Hua Wen, Zi-Jing Zhang, Shuai Li, Jin Song, Liu-Zhu Gong
Summary: The authors have developed a method to construct four stereoisomers of oxindoles with high enantioselectivity and diastereoselectivity using cooperative copper- and organocatalysis. The ability to precisely control the reactive site planar in the region is of great importance in asymmetric stereodivergent catalysis. This method provides a new strategy for the synthesis of chiral functional molecules and has potential applications in alkaloid synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Meng-Ying Hao, Yin Zhang, Na Lin, Rong Fu, Xiao-Shuang Ji, Bo Jiang, Shu-Jiang Tu, Wen-Juan Hao
Summary: A new gold(i) self-relay catalysis reaction has been reported, which enables the annulative oxygenation of propargylic alcohols with various O-nucleophiles, producing functionalized benzofurans in moderate to good yields under mild conditions. This protocol boasts the pi- and sigma-Lewis acid capability of gold complexes, showcasing high molecular convergence, broad substrate flexibility, high functional group compatibility, and mild conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Mengwei You, Yan Li, Xin Lv, Guodong Shen, Xiao Xiao, Liejin Zhou
Summary: A practical and useful method for the synthesis of enantioenriched spirofuro[2,3-b]azepine-5,3 & PRIME;-indoline derivatives was developed. This method involves cycloisomerization/asymmetric formal [4 + 3] cycloaddition reactions using enyne-amides and isatin-derived enals under gold(i)/chiral N-heterocyclic carbene (NHC) relay catalysis, resulting in high stereoselectivity (dr > 20 : 1, up to 96% ee) and good functional-group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Guifang Chen, Bo Xu
Summary: The oxidative addition of Au-I with aromatic iodide can generate reactive and functional group tolerant Au-III catalysts. These catalysts show different reactivity compared to Au-I catalysts and other transition metal catalysts. We demonstrated the synthesis of sulfonyl quinolines, formyl indoles, and quinolones using this catalytic system, which exhibited good chemo- and regioselectivity and could be conducted in the open air.
Article
Chemistry, Multidisciplinary
Akira Matsumoto, Yoko Shiozaki, Shunya Sakurai, Keiji Maruoka
Summary: A catalytic method for the synthesis of functionalized aliphatic acid esters using silylperoxyacetals has been developed, leading to the efficient synthesis of pharmaceutically important compounds and structurally diverse hydroxy acid derivatives via a C-O bond formation process utilizing TEMPO.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Correction
Chemistry, Inorganic & Nuclear
Firdaus Rahaman Gayen, Abdul Aziz Ali, Debashree Bora, Saptarshi Roy, Supriya Saha, Lakshi Saikia, Rajib Lochan Goswamee, Biswajit Saha
Summary: This study focuses on the synthesis and characterization of a ferrocene functionalized Schiff base containing Cu(II) complex, and demonstrates its catalytic activity in the azide alkyne cycloaddition reaction at parts-per-million levels.
DALTON TRANSACTIONS
(2021)
Article
Biochemistry & Molecular Biology
Sourav Nayak, Somnath Yadav
Summary: We report a direct method for converting anomeric hydroxides to glycosyl azides using diphenyl-phosphoryl azide. Protecting group manipulations on the hexose sugars allowed for the stereoselective synthesis of either alpha-glycosyl azides or 8-anomeric azides in moderate to very good yields. The reaction was also successfully used for the synthesis of 8-2-deoxy-2-aminoglucosyl azides.
CARBOHYDRATE RESEARCH
(2023)
Article
Multidisciplinary Sciences
John M. Ovian, Petra Vojackova, Eric N. Jacobsen
Summary: Asymmetric transition-metal catalysis is a powerful strategy for producing enantiomerically enriched molecules. The traditional strategy for inducing enantioselectivity involves using chiral ligands to create a reactive metal site that promotes the formation of the major enantiomer and inhibits the formation of the minor enantiomer. However, this approach has limitations in certain scenarios. This study introduces a new approach that utilizes neutral hydrogen-bond donors to achieve enantioselectivity through ion pairing and non-covalent interactions. The results demonstrate high enantioselectivity in intramolecular ruthenium-catalyzed propargylic substitution reactions.
Article
Chemistry, Organic
Xianfu Fang, Tianyang Zhang, Wei Fang, Gong Zhang, Yangfeng Li, Yizhou Li
Summary: A practical and general synthetic strategy was developed to construct a medicinally important 5-amino-1,2,3-triazole moiety on DNA by coupling DNA-conjugated azides and monosubstituted acetonitriles via azide-acetonitrile click reaction. This DNA-compatible reaction could be employed in practical DNA-encoded library (DEL) construction and potentially expand the chemical space of DNA-encoded libraries.
