Article
Chemistry, Applied
Julien Coulomb
Summary: Aluminum chloride-promoted Conia-ene-related cyclization of & alpha;,β-unsaturated enones with unactivated olefin at the ε-, ζ- or η-position resulted in the formation of unsaturated decalones or hexahydroindenones in good yields. Cyclopropanes could be utilized as olefin surrogates, leading to the same bicyclic products with slightly improved efficiency. This method enables the synthesis of a wide range of bi- or tricyclic enone synthons, some of which have potential applications as odorants or in the synthesis of bioactive molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Dong-Ai Li, Xiang-Hong He, Xue Tang, Yuling Wu, Hongli Zhao, Gu He, Cheng Peng, Bo Han, Gu Zhan
Summary: This study successfully developed an efficient strategy for synthesizing spirocyclo-penteneoxindoles, which have potential biological activity. Using the thiourea/silver dual catalytic reaction of 2-(2-oxoindolin-3-yl)malononitrile with ortho-ethynyl substituted nitrostyrene in a (3 + 2)/Conia-ene type reaction, three new C-C bonds were formed within one synthetic step. The yield and selectivity of the indane-fused spirocyclopenteneoxindoles were excellent.
Review
Chemistry, Multidisciplinary
En-Ze Lin, Yin Xu, Kegong Ji, Long-Wu Ye
Summary: Conia-ene reactions, an emerging field in synthetic chemistry, have gained significance in recent years due to their high efficiency and atom economy in building valuable cyclic molecules. The rapid development of transition-metal catalysis and organocatalysis has greatly impacted the exploration of asymmetric Conia-ene reactions, leading to the development and successful application of various strategies. Organized based on catalytic systems, recent progress in this area has been comprehensively summarized to highlight the features, practicalities, and possible mechanistic rationale of the reactions.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Physical
Chuncheng Zou, Lei Yang, Lei Zhang, Chengyu Liu, Yueyue Ma, Gonghua Song, Zhen Liu, Ruihua Cheng, Jinxing Ye
Summary: The study introduces a method for the synthesis of chiral all-carbon spirocycles catalyzed by a silver(I)/bisdiamine complex, with DFT calculations confirming its high catalytic activity and enantioselectivity. Additionally, various polycyclic products can be obtained through derivatization of the spirocyclic enones.
Article
Chemistry, Multidisciplinary
Christina Jaeger, Mona Haase, Katja Koschorreck, Vlada B. Urlacher, Jan Deska
Summary: Biocatalytic oxidation of acylated hydroxylamines enables selective introduction of nitrogen functionalities by activating allylic C-H bonds. Utilizing laccases or oxidase/peroxidase couple with air as the oxidant, acylnitroso species are generated under mild aqueous conditions. These reactive intermediates undergo C-N bond formation through an ene-type mechanism, providing high yields in both intramolecular and intermolecular enzymatic aminations. Investigations on different pathways and labelling studies provide insight into the promiscuity of oxidoreductases as catalysts for nitroso-based transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Christoph Etling, Giada Tedesco, Markus Kalesse
Summary: This study investigated the different reactivity of trienones under Lewis and Bronsted acids catalysis, resulting in novel Nazarov cyclization tandem reactions terminating oxyallyl cations by ene-type reactions. The bicyclic spiro compounds produced were shown to be useful intermediates for further functionalization. Furthermore, the tandem Nazarov/ene cyclization was found to be preferred over a Nazarov/[3+2] tandem reaction for all substrates, regardless of chain length.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Na Wang, Li-Wen Fan, Jin Zhang, Qiang-Shuai Gu, Jin-Shun Lin, Guo-Qiang Chen, Xin-Yuan Liu, Peiyuan Yu
Summary: This study investigates the highly enantioselective intramolecular hydroamination reaction and uncovers its uncommon reaction mechanism. The reactivity of this reaction is primarily determined by the substituents on the internal carbon of the alkene, as well as the substituents on the terminal alkene carbons. The lower acidity of chiral phosphoric acids compared to chiral NTPAs results in a slower reaction.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Haotian Zhao, Yu Lin, Mingyu Jiang, Bo Su
Summary: We report a general synthetic strategy for the synthesis of diverse boromethylene cyclobutanes and spiro-boromethylene cyclobutanes. This strategy enables the installation of various functionalities at each site on the cyclobutane skeleton with defined stereochemistry and introduces a versatile boromethylene unit that can be easily transformed to new functional groups. The concise and divergent total syntheses of four cyclobutane-containing natural products were achieved using this strategy.
Article
Chemistry, Organic
Shangyuan Wang, Jiajun Zhao, Jun Ying, Xiao-Feng Wu
Summary: This study developed a palladium-catalyzed one-pot two-step radical mediated carbonylative cyclization method to construct polycyclic 3,4-dihydroquinolin-2-(1H)-one scaffolds using perfluoroalkyl iodides and Mo-(CO)(6) with 1,7-enynes. Various polycyclic 3,4-dihydroquinolin-2-(1H)-one derivatives containing perfluoroalkyl and carbonyl units were synthesized with high yields. Moreover, modification of several bioactive molecules was demonstrated using this protocol.
Article
Chemistry, Multidisciplinary
Lantian Sun, Junrong Huang, Bo Wang, Guangyan Du, Chi-Sing Lee
Summary: An asymmetric formal synthesis of (+)-phomactin A has been successfully accomplished. The key steps in the synthetic strategy include establishing the AB ring system in one-pot via Prins/Conia-ene cascade cyclization reaction and the C ring formation via gamma-hydroxylation of enone in the late-stage of the synthesis. The two major fragments are readily prepared from (+)-pulegone and geraniol, respectively, using specific strategies.
Article
Multidisciplinary Sciences
Dongquan Zhang, Miaomiao Li, Jiajia Li, Aijun Lin, Hequan Yao
Summary: The article translated above introduces a novel application of the Alder-ene reaction, achieving enantioselective reactions between cyclopentenes and silylacetylenes through rhodium catalysis, leading to the synthesis of compounds with chiral carbon centers.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ruize Ma, Yang Chen, Songjia Fang, Huanfeng Jiang, Shaorong Yang, Wanqing Wu
Summary: In this study, a straightforward method to synthesize alkenyl dihydrofurans via palladium-catalyzed acetalization/annulation from conjugated enynones and alcohols is reported. The reaction involves a 5-exo-dig cyclization process, leading to the formation of four new chemical bonds including two carbon-halogen bonds on the exocyclic alkenyl group. Preliminary mechanistic studies suggest the involvement of the haloalkyne generated in situ in this transformation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Fusheng Bie, Chengwei Liu, Michal Szostak, Xuejing Liu
Summary: A robust palladium-catalyzed decarbonylative alkynylation of aryl anhydrides is reported. The catalytic system of Pd(OAc)(2)/XantPhos and DMAP as a nucleophilic additive has been identified as effective promoters for decarbonylative Sonogashira alkynylation. The present process expands this reactivity to readily available aryl anhydrides as electrophilic reagents for decarbonylative alkynylation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Tianmei Zhang, Min Cai, Wenfeng Zhao, Mao Liu, Nan Jiang, Qingmei Ge, Hang Cong
Summary: We developed a practical and efficient electrochemical approach for the synthesis of pi-conjugated phosphonium salts through intramolecular annulation and C-P bond construction. This reaction took place under catalyst- and adscititious oxidant-free conditions at room temperature. A variety of substituted pi-conjugated phosphonium salt products were obtained with good functional group tolerance and yields. A gram-scale reaction demonstrated the potential of this protocol for practical applications. Preliminary mechanistic studies suggested the involvement of free radicals in this process.
Article
Chemistry, Organic
Zhidong Jiang, Jianhui Zhou, Haoran Zhu, Hong Liu, Yu Zhou
Summary: A novel Rh(III)-catalyzed C-H activation/annulation cascade of indole-enaminones with diazo compounds was reported, generating diversely functionalized carbazole frameworks with good to excellent yields. The most notable feature is the formation of a novel [5 + 1] cyclization product, accompanied by the complete removal of acetyl and N,N-dimethyl groups from the substrates, rather than the expected [4 + 2] cyclization products.
