Article
Chemistry, Physical
Lin-Jun Qi, Chong-Yang Shi, Peng-Fei Chen, Long Li, Gang Fang, Peng-Cheng Qian, Chao Deng, Jin-Mei Zhou, Long-Wu Ye
Summary: The study presents a novel gold-catalyzed 1,1-carboalkoxylation method for the synthesis of valuable cyclic compounds, enabling asymmetric synthesis through a chirality-transfer strategy. Further mechanistic insight into the distinct migration into gold carbenes is supported by theoretical calculations.
Article
Chemistry, Organic
Ju Eun Jeon, Siyeon Jeong, Hayeon Kwak, Jung Min Joo
Summary: In this study, gold(III)-catalyzed cyclization reactions of alkynyl norbornene derivatives were developed to generate benzofused (hetero)arenes with substitutions at the benzocyclic ring. The combination of Au(OAc)(3) and AgNTf2 allowed for the annulation of (hetero)arenes by intramolecular hydro(hetero)arylation followed by retroDiels-Alder reactions to afford fully conjugated benzofused (hetero)arenes in higher yields than the previously developed Pd(OAc)(2)-catalyzed protocol. Additionally, using AuCl3 instead of Au(OAc)(3) led to a rearrangement of (hetero)arenes with the norbornene bridge installed at the more electron-rich and sterically demanding position to afford the corresponding regioisomeric products in a divergent manner. These results highlight the importance of steric effects in addition to the electronic effects of the catalyst and the substrate on the rearrangement.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Bo-Han Zhu, Ying-Qi Zhang, Hao-Jin Xu, Long Li, Guo-Cheng Deng, Peng-Cheng Qian, Chao Deng, Long-Wu Ye
Summary: An efficient copper-catalyzed tandem alkyne hydration/intramolecular Mannich reaction has been investigated for the synthesis of valuable compounds. This method allows the efficient synthesis of 3,4-dihydro-2-quinolones with high regio-, diastereo-, and enantioselectivity.
Article
Chemistry, Multidisciplinary
Hiroki Tashiro, Masahiro Terada, Itaru Nakamura
Summary: Gold-catalyzed reactions were used to synthesize 2H-azirines with sulfenyl and acyl groups at the 3-position, yielding good to excellent results. These reactions involved internal transfer of sulfinyl oxygen atom and carbene insertion into the N-S bond for ring construction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Nengneng Zhou, Qiankun Xu, Ziqin Xia, Kaimo Kuang, Sixin Wu, Wenping Li, Man Zhang
Summary: In this study, a novel palladium-catalyzed radical cascade reaction was developed for the synthesis of cyanoalkylsulfone-containing cyclopenta[gh]phenanthridines. The reaction involved the cleavage of a C-C single bond and insertion of SO2, and showed mild reaction conditions, a broad substrate scope, and high functional group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Yin Xu, Gan-Lu Qian, Da-Qiu Cui, Peng-Cheng Qian, Chao-Yue Zhao, Xin Hong, Bo Zhou, Long-Wu Ye
Summary: Herein, a chiral Bronsted acid-catalyzed desymmetrization reaction of diynes is reported, providing a facile access to enantioenriched 1,3-diaminopropanol derivatives and γ-butyrolactones with high enantioselectivities. These products can be used as precursors for the synthesis of versatile N- and O-heterocycles, which are important structural cores of bioactive molecules. Control experiments and theoretical calculations are used to confirm the mechanism and elucidate the origin of enantioinduction.
Article
Chemistry, Multidisciplinary
Shangbiao Zhang, Yan Gao, Rui Xiao, Yang Li, Yanan Wang, Zheliang Yuan
Summary: In this study, a tandem synthesis of various CF3Se-containing heterocyclic compounds was developed using Tf2O as the catalyst and trifluoromethyl selenoxides as the electrophilic trifluoromethylselenolation reagents. The process is characterized by its mild conditions, easy operation, and good functional group compatibility. A variety of alkynes were successfully transformed into CF3Se-containing indoles, benzofurans, benzothiophenes, isoquinolines, and chromenes in good yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Juan Zhang, Zhi-Guang Ma, Yu Tian, Wei Li, Wen-Chao Gao, Hong-Hong Chang
Summary: In this study, a divergent synthesis of CF3-substituted allenes, cyclopentenes, alkynes, and fluorinated enynes was achieved via regioselective nucleophilic addition of carbon nucleophiles to 2-trifluoromethyl-1,3-enynes, with the promotion of inorganic base K3PO4.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Gilson Zeni, Benhur Godoi, Carla K. Jurinic, Andrei L. Belladona, Ricardo F. Schumacher
Summary: This manuscript provides an overview of the most recent advances in the synthesis of carbo- and heterocycles through reactions of alkynes with organyl chalcogenides under metal-free conditions. Methods discussed include the use of electrophilic chalcogenyl halides and radical cyclization protocols utilizing electrochemical oxidative conditions, light-induced photoredox catalysis, or mild oxidants.
Article
Chemistry, Organic
Leilei Cao, Liliang Huang, Xianjun Xu, Erik V. Van der Eycken, Huangdi Feng
Summary: A novel method for the construction of nitrogen-tethered 1,6-enynes with high atom economy and exclusive chemoselectivity has been developed. Experimental studies suggest that the key step in this methodology is the alkyne-iminium ene reaction involving an intermolecular hydride transfer.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yan He, Qimeng Liu, Tian Gong, Yunfei Liu, Xinying Zhang, Xuesen Fan
Summary: A convenient synthesis protocol for alpha-substituted-beta-oxo azaheterocycles has been developed using oxoammonium salt-promoted cascade reaction. Nucleophiles such as acetyl or cyano group-containing active methylene compounds or morpholines were reacted with saturated cyclic amines, leading to the formation of different intermediates. The chemoselectivity of these reactions was investigated through experimental studies and DFT calculations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Guang-Yu Zhu, Ji-Jia Zhou, Li-Gao Liu, Xiao Li, Xin-Qi Zhu, Xin Lu, Jin-Mei Zhou, Long-Wu Ye
Summary: A catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides has been described, enabling the divergent and atom-economic synthesis of valuable medium-sized N,S-heterocycles with moderate to good yields and broad substrate scope. Excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Theoretical calculations have been employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Da-Ping Jin, Shi-Qi Cao, Fu Cheng, Ze-Sen Xue, Run-Ze Li, Yan-Lin Pu, Dao-Yong Zhu, Wen Bao, Xue-Tao Xu, Shao-Hua Wang
Summary: An Au(I)-catalyzed cascade reaction involving cyclization and semipinacol rearrangement of 1,6-enynes has been developed for the synthesis of spiro[4.5]decanes and 7-azaspiro[4.5]decanes. The use of JohnPhosAuCl/NaBARF catalyst led to the formation of functionalizable spirocyclic products with high diastereoselectivity ranging from 6.7:1 to > 20:1 dr. A plausible reaction mechanism has been proposed based on previous literature and experimental findings.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Angelica R. Claus, Tales A. C. Goulart, Davi F. Back, Gilson Zeni
Summary: In this study, a regio- and stereoselective synthesis of alpha-methylene-beta-lactams was reported via a 4-exo-dig-cyclization of N-benzyl-N-methyl-propiolamides catalyzed by a base. Experimental evidence suggests that the transformation proceeds through a concerted ionic cyclization, followed by protonation of the vinyl species promoted by tert-butanol. The obtained alpha-methylene-beta-lactams were suitable substrates for the Heck coupling conditions, leading to the formation of corresponding products through carbon-carbon bond formation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Marina Yu. Dvorko, Dmitrii A. Shabalin, Igor A. Ushakov, Elena Yu. Schmidt, Boris A. Trofimov
Summary: The cascade dimerization of alkynones with sterically hindered secondary alkyl groups at the carbonyl function unexpectedly produced highly functionalized furans. This reaction efficiently takes place at room temperature in the presence of a potassium tert-butoxide/dimethylsulfoxide superbase catalytic system. Alkynones with an additional C-H active site at the carbon-carbon triple bond followed a different dimerization pathway to form 3-alkenylpyran-4-ones. The discovery of these reactions expands the traditional understanding of alkynone reactivity in strong basic conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
