☆ 4.7 Article

Spirocyclopropanation Reaction of para-Quinone Methides with Sulfonium Salts: The Synthesis of Spirocyclopropanyl para-Dienones

JOURNAL OF ORGANIC CHEMISTRY (2016)

期刊

JOURNAL OF ORGANIC CHEMISTRY

卷 81, 期 6, 页码 2598-2606

出版社

AMER CHEMICAL SOC

DOI: 10.1021/acs.joc.5b02725

关键词

-

类别

Chemistry, Organic

资金

National Natural Science Foundation of China [21572083, 21322201, 21290180]
Fundamental Research Funds for the Central Universities [lzujbky-2015-48, lzujbky-2013-ct02]
State Key Laboratory of Natural and Biomimetic Drugs [K20150213]
PCSIRT [IRT_15R28]
111 Project of Ministry of Education of China [111-2-17]
Chang Jiang Scholars Program

向作者/读者索取更多资源

Protocol

Reagent

摘要

A novel DBU-mediated stereoselective spirocyclopropanation of para-quinone methides with sulfonium salts has been developed on the basis of the mode involving a 1,6-conjugate addition/intramolecular dearomatizing cyclization cascade. This reaction provides a mild and effective method for the assembly of synthetically and structurally interesting spirocyclopropanyl para-dienones. The feasibility for the enantioselective access to such functionalized para-dienones has also been explored by using the axially chiral sulfonium salt. Importantly, the regioselective ring openings of the related spirocyclopropanyl para-dienones have been achieved divergently.

作者

我是这篇论文的作者

点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.7

评分不足

次要评分

新颖性

-

重要性

-

科学严谨性

-

评价这篇论文

推荐

Article Chemistry, Organic

Bronsted Acid-Catalyzed Formal (3+3)-Annulation of Propargylic (Aza)-para-Quinone Methides with 4-Hydroxycoumarins and 1,3-Dicarbonyl Compounds

Zong-Wang Qiu, Xue-Tao Xu, Han-Peng Pan, Zhen-Sheng Jia, Ai-Jun Ma, Jin-Bao Peng, Ji-Yuan Du, Na Feng, Bao Qiong Li, Xiang-Zhi Zhang

Summary: In this study, a highly efficient catalytic method was reported for the formal (3+3)-annulation of (aza)-para-quinone methides generated in situ from propargylic alcohols with 4-hydroxycoumarins and 1,3-dicarbonyl compounds under the catalysis of a Bronsted acid. The method provides a practical access to synthetically important and highly functionalized pyranocoumarins and pyrans in excellent yields under mild conditions, which exhibit significant inhibitory activity toward alpha-glucosidase.

JOURNAL OF ORGANIC CHEMISTRY (2021)

添加到收藏夹

Article Chemistry, Organic

Fluorohydroxylation and Hydration Reactions of para-Quinone Methides Promoted by Selectfluor

Lei Dai, Zhou Zhang, Guangzhou Zhu, Yun Liu, Xiaoqin Liu, Jinpeng Zhang, Liangce Rong

Summary: This article describes the Selectfluor-promoted vicinal fluorohydroxylation and hydration reaction of para-quinone methides (p-QMs), which affords vicinal fluorohydrins and ketone/ether products in high yields. The electronic properties of substituents in the aromatic ring highly control the hydration products, and the amount of Selectfluor is significantly different during the synthesis of ketone/ether products. This reaction also marks the first fluorohydroxylation of p-QMs, and the wide range of p-QMs makes the vicinal fluorohydroxylation of great significance.

JOURNAL OF ORGANIC CHEMISTRY (2023)

添加到收藏夹

Article Chemistry, Multidisciplinary

Synthesis of spiroindolenine-bearing chroman scaffolds based on a cyclization reaction of para-Quinone methides

Hongmei Qin, Qimei Xie, Long He

Summary: An efficient diastereoselective cyclization reaction was developed to synthesize spiroindolenine-bearing chroman scaffolds, which incorporated two pharmacophores, namely chroman and spiroindoline.

NEW JOURNAL OF CHEMISTRY (2022)

添加到收藏夹

Article Chemistry, Organic

Diastereoselective 1,6-Addition of α-Phosphonyloxy Enolates to para-Quinone Methides

Amjad Ali, Raveena Jajoria, Harish K. Harit, Ravi P. Singh

Summary: In this study, the addition of alpha-ketoamide top-quinone methide initiated by dialkylphosphite in the presence of organic base DBU was explored. The coupling of dialkylphosphites to alpha-ketoamides followed[1,2]-phospha-Brook rearrangement, generating alpha-phosphonyloxy enolates that were subsequently seized by p-quinonemethides. This two-step one-pot 1,6-conjugate addition method provides effective access to a series of isatin-incorporated phosphate-bearing 1,6-adducts with high yield and selectivity.

JOURNAL OF ORGANIC CHEMISTRY (2022)

添加到收藏夹

Article Chemistry, Organic

Formal [4+1] Cyclization of ortho- or para-Quinone Methides with 3-Chlorooxindoles: Synthesis of 3,2′-Tetrahydrofuryl Spirooxindoles

Xiaochen Tian, Xiaoli Zhang, Xiaohan Hou, Weiwu Ren, Xiaoyang Li, Fei Zhao, Houchao Tao, Yang Wang

Summary: A base-promoted formal [4+1] cycloaddition of ortho- and para-quinone methides with 3-chlorooxindoles has been reported to provide various functionalized 3,2'-tetrahydrofuryl spirooxindoles in high yields under mild conditions. Unexpected reversal in diastereoselectivity was observed in these reactions. Computational studies have revealed the origin of the diastereoselectivity, showing that different configurations of 1,4-addition and 1,6-addition at the oxindole carbanionic center result in different diastereomers. The anti-tumor activity of these structurally unique spirooxindole derivatives has been reported.

ASIAN JOURNAL OF ORGANIC CHEMISTRY (2021)

添加到收藏夹

Article Chemistry, Organic

Atroposelective Synthesis of Axially Chiral Styrenes Connecting an Axially Chiral Naphthyl-indole Moiety Using Chiral Phosphoric Acid Catalysis

Alemayehu Gashaw Woldegiorgis, Haorui Gu, Xufeng Lin

Summary: The organocatalytic asymmetric reactions of C2-unsubstituted racemic naphthyl-indoles with orthoalkynylnaphthols were used to synthesize axially chiral styrenes connected to an axially chiral naphthyl-indole unit. By employing chiral phosphoric acid as the catalyst, these axially chiral styrenes were obtained in good yields (up to 96%) and excellent stereoselectivity (up to >99.9% ee, >20:1 dr, and >99:1 E/Z) under mild conditions. Furthermore, further synthetic transformations were achieved with high yields and excellent stereocontrol.

ORGANIC LETTERS (2023)

添加到收藏夹

Review Chemistry, Physical

Asymmetric Catalytic Transformations of Aza-ortho- and Aza-para-Quinone Methides

Mercedes Zurro, Aitor Maestro

Summary: This paper reviews the recent literature on the catalytic methodologies for the derivatization of aza-QM, including organocatalytic and organometallic approaches. The review analyzes various catalytic systems, involving chiral NHC carbenes, phosphoric acids, phosphoramidites, phosphine, copper, and palladium catalysis, showcasing their applicability for the synthesis of a diverse array of N-containing compounds, many of which exhibit biological activity.

CHEMCATCHEM (2023)

添加到收藏夹

Article Chemistry, Organic

DMAP Mediated Efficient Construction of Functionalized Chromenes through One-Pot Reaction of para-Quinone Methides with Allenoates

Zefeng Song, Yuping Jia, Daizhou Zhang, De Wang

Summary: A novel DMAP-mediated Rauhut-Currier/oxa-Michael addition cascade reaction was reported for the first time, resulting in a series of functionalized chromenes from the reaction of hydroxylphenyl-substituted para-quinone methide with allenoate. The chromene products obtained in moderate to good yields under this one-pot cascade reaction could be easily transformed into different derivatives, and a plausible mechanism was proposed to elucidate this novel reaction.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2021)

添加到收藏夹

Article Chemistry, Organic

Addition of sulfonylphthalides to para-quinone methides: Selective 1,6-additions and oxidative annulations

Kavyashree Kuppayya Gond, Mahagundappa Rachappa Maddani

Summary: In this study, isochroman-1,4-diones and addition products were selectively synthesized through KOBu-Catalyzed addition of sulfonylphthalides to p-quinone methides. It is noteworthy that isochroman-1,4-diones were obtained via an unprecedented oxidative annulation pathway. The research highlights the broad substrate scope, high yields, shorter reaction time, and mild reaction conditions. Furthermore, some addition products can be transformed into functionalized heterocyclic molecules. Additionally, the scalability experiment demonstrates the practical feasibility of preparing isochroman-1,4-diones in larger scale reactions.

ORGANIC & BIOMOLECULAR CHEMISTRY (2023)

添加到收藏夹

Article Medicine, Research & Experimental

Design, synthesis and antitumor activity of potent and safe para-quinone methides derivatives in vitro and in vivo

Pengxiao Li, Yazhong Ma, Ke Wang, Xiaohan Shi, Jie Yang, Guoyun Liu

Summary: The cytotoxicity of para-quinone methides (p-QMs) derivatives was investigated against cancer cells, and it was found that substituents in the ortho-position of the phenyl ring significantly enhanced the cytotoxicity. Further studies revealed that this cytotoxicity originated from the ability of p-QMs derivatives to generate ROS, leading to disruption of redox balance and induction of apoptosis.

BIOMEDICINE & PHARMACOTHERAPY (2022)

添加到收藏夹

Article Chemistry, Multidisciplinary

Organocatalytic Asymmetric Dearomatizing Hetero-Diels-Alder Reaction of Nonactivated Arenes

Kai Li, Shengli Huang, Tianyu Liu, Shiqi Jia, Hailong Yan

Summary: We demonstrated an organocatalytic asymmetric dearomatizing hetero-Diels-Alder reaction of benzene derivatives, which allows the synthesis of diverse stereochemically complex compounds and oxahelicenes. The high complexity and three-dimensionality of the products are crucial for their potential applications in materials science and drug discovery.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

添加到收藏夹

Article Chemistry, Organic

Synthesis of Phenolic Coumestans via a Sequential Dehydrogenation/Oxa-Michael Addition Reaction of 2?,4?-Dihydroxyl-3-arylcoumarins

Qinfang Yan, Yi Jiang, Xianheng Song, Guoqing Lu, Qianzhong Zhang, Zhibo Du, Albert S. C. Chan, Yong Zou

Summary: A facile and practical approach for the synthesis of natural coumestans and derivatives starting from 2',4'-dihydroxyl-3-arylcoumarins has been developed. The process involves a sequential intramolecular dehydrogenation/oxa-Michael reaction efficiently promoted by 1,8-diazabicyclo[5.4.0]undec-7-ene at 40 degrees C under metal- and ligand-free conditions with good functional group compatibility.

JOURNAL OF ORGANIC CHEMISTRY (2022)

添加到收藏夹

Article Chemistry, Organic

Electrochemical Radical δ-H Sulfonylation Reaction for the Synthesis of 4-((Aryl,Arylsul fonyl)methylene)-2,5-Cyclohexadiene Derivatives

Lei Dai, Qiuyu Yu, Jinghang Zhang, Fan Wu, Chang Wang, Jinpeng Zhang, Liangce Rong

Summary: An efficient electrochemical radical delta-H sulfonylation reaction of para-quinone methides and sodium sulfinates has been achieved under common laboratory conditions. The reaction allows for the construction of a new C(sp(2))-S bond to synthesize 4-((aryl,arylsulfonyl)methylene)-2,5-cyclohexadiene derivatives with a broad substrate scope and good functional group tolerance. Further studies have shown that the reaction exhibits excellent regional selectivity.

JOURNAL OF ORGANIC CHEMISTRY (2021)

添加到收藏夹

Article Chemistry, Organic

Synthesis of 6H-Benzo[c]chromene Scaffolds from O-Benzylated Phenols through a C-H Sulfenylation/Radical Cyclization Sequence

Steve Karreman, Simon B. H. Karnbrock, Sebastian Kolle, Christopher Golz, Manuel Alcarazo

Summary: The synthesis of S-aryl dibenzothiophenium salts and their transformation into 6H-benzo[c]chromenes is achieved through a highly selective reaction pathway, involving photocatalytic single-electron transfer and cyclization of radical intermediates. The mechanistic studies reveal a kinetically favored cyclization pathway and subsequent ring expansion towards the desired tricyclic systems.

ORGANIC LETTERS (2021)

添加到收藏夹

Article Biochemistry & Molecular Biology

One-Pot Synthesis of 3,4-Dihydrocoumarins via C-H Oxidation/Conjugate Addition/Cyclization Cascade Reaction

Dae Young Kim

Summary: A one-pot strategy has been developed for the synthesis of multisubstituted 3,4-dihydrocoumarins with high yields and excellent diastereoselectivity. This approach involves C-H oxidation and cyclization cascade reactions of 2-alkyl phenols and oxazolones in the presence of silver oxide and p-toluenesulfonic acid as catalysts.

MOLECULES (2023)

添加到收藏夹

Article Chemistry, Organic

Synthetic studies toward melotenine A

Ji-Yuan Du, Xian-Tao An, Xian-He Zhao, Xiao-Yan Ma, Ye-Xing Cao, Chun-An Fan

TETRAHEDRON (2019)

添加到收藏夹

Article Chemistry, Organic

Asymmetric Organocatalytic Synthesis of 2,3-Allenamides from Hydrogen-Bond-Stabilized Enynamides

Zhi-Gang Ma, Jie-Lu Wei, Jun-Bing Lin, Guan-Jun Wang, Jia Zhou, Kai Chen, Chun-An Fan, Shu-Yu Zhang

ORGANIC LETTERS (2019)

添加到收藏夹

Article Chemistry, Organic

CuH-Catalyzed Asymmetric 1,6-Conjugate Reduction of p-Quinone Methides: Enantioselective Synthesis of Triarylmethanes and 1,1,2-Triarylethanes

Ting Pan, Pan Shi, Bo Chen, Da-Gang Zhou, Ya-Li Zeng, Wen-Dao Chu, Long He, Quan-Zhong Liu, Chun-An Fan

ORGANIC LETTERS (2019)

添加到收藏夹

Article Chemistry, Multidisciplinary

Asymmetric Catalytic [4+5] Annulation of ortho-Quinone Methides with Vinylethylene Carbonates and its Extension to Stereoselective Tandem Rearrangement

Xian-Tao An, Ji-Yuan Du, Zhi-Long Jia, Qing Zhang, Ke-Yin Yu, Yi-Zhou Zhang, Xian-He Zhao, Ran Fang, Chun-An Fan

CHEMISTRY-A EUROPEAN JOURNAL (2020)

添加到收藏夹

Article Chemistry, Organic

Palladium-Catalyzed Asymmetric (2+3) Annulation of p-Quinone Methides with Trimethylenemethanes: Enantioselective Synthesis of Functionalized Chiral Spirocyclopentyl p-Dienones

Zhi-Long Jia, Xian-Tao An, Yu-Hua Deng, Hui-Bin Wang, Kang-Ji Gan, Jing Zhang, Xian-He Zhao, Chun-An Fan

ORGANIC LETTERS (2020)

添加到收藏夹

Article Chemistry, Organic

P(NMe2)3-Mediated Umpolung Spirocyclopropanation Reaction of p-Quinone Methides: Diastereoselective Synthesis of Spirocyclopropane-Cyclohexadienones

Yu-Hua Deng, Wen-Dao Chu, Yun-Han Shang, Ke-Yin Yu, Zhi-Long Jia, Chun-An Fan

ORGANIC LETTERS (2020)

添加到收藏夹

Article Chemistry, Organic

Palladium-Catalyzed Asymmetric (4+2) Annulation of γ-Methylidene-δ-valerolactones with Alkenes: Enantioselective Synthesis of Functionalized Chiral Cyclohexyl Spirooxindoles

Zhi-Long Jia, Xian-Tao An, Yu-Hua Deng, Lin-Han Pang, Chun-Fang Liu, Le-Le Meng, Jia-Kun Xue, Xian-He Zhao, Chun-An Fan

Summary: An unprecedented asymmetric catalytic (4 + 2) annulation reaction has been developed for the synthesis of chiral cyclohexadienone-fused cyclohexyl spirooxindoles using aryl-substituted gamma-methylidene-delta-valerolactones (GMDVs) and isatin-derived para-quinone methides (p-QMs) catalyzed by palladium(0) and (S,S,S)-(-)-Xyl-SKP. This reaction can efficiently and selectively forge three highly congested contiguous tetrasubstituted carbon atoms, including two vicinal quaternary stereogenic centers.

ORGANIC LETTERS (2021)

添加到收藏夹

Article Chemistry, Multidisciplinary

Hypervalent-Iodine(III)-Mediated Tandem Oxidative Dearomatization/Aziridination of Phenolic Amines: Synthesis of Functionalized Unactivated Aziridines

Ye-Xing Cao, Patamawadee Silalai, Chun-Fang Liu, Ke-Yin Yu, Xu Bao, Xian-He Zhao, Rungnapha Saeeng, Chun-An Fan

Summary: This study presents a novel hypervalent-iodine(III)-mediated tandem reaction for the synthesis of structurally interesting and synthetically useful aziridines. The resulting densely functionalized aziridines offer a platform for accessing architecturally diverse aza-heterocycles through selective ring-opening transformations initiated by the reaction.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

添加到收藏夹

Article Chemistry, Organic

Tandem (2+2) Annulation/Retro-4π Electrocyclization/Imino-Nazarov Cyclization Reaction of p-Quinone Methides with Ynamides: Expeditious Construction of Functionalized Aminoindenes

Ke-Yin Yu, Yu-Hua Deng, Xiao-Min Ge, Xian-Tao An, Peng-Fei Shu, Ye-Xing Cao, Xian-He Zhao, Chun-An Fan

Summary: A new tandem annulation reaction between p-quinone methides and ynamides has been described, resulting in the synthesis of functionalized aminoindene compounds. The reaction involves a unique structural rearrangement of p-QMs, with cleavage of the C5-C6 bond and late-stage formation of the C4-C6 bond, leading to the development of a methodology for constructing functionalized aminoindenes.

ORGANIC LETTERS (2021)

添加到收藏夹

Article Chemistry, Organic

Copper-Catalyzed (4+1) Cascade Annulation of Terminal Alkynes with 2-(Tosylmethyl)anilines: Synthesis of 2,3-Disubstituted Indoles

Xu Yan, Chun-Fang Liu, Xian-Tao An, Xiao-Min Ge, Qing Zhang, Lin-Han Pang, Xu Bao, Chun-An Fan

Summary: A novel strategy based on Cu-catalyzed (4+1) cascade annulation of terminal alkynes with 2-(tosylmethyl)anilines has been developed for the expeditious synthesis of 2,3-disubstituted indoles, involving in situ generations of aza-o-quinone methides and alkynyl-copper(I) species. This annulation provides an effective method for the assembly of synthetically and structurally interesting 2,3-disubstituted indoles.

ORGANIC LETTERS (2021)

添加到收藏夹

Article Chemistry, Organic

Catalytic Enantioselective Desymmetrization of Prochiral Triacylamines via Pseudopeptidic Guanidine-Guanidinium Catalysis

Hu Qu, Xin-Shen Liang, Wen-Juan Wang, Xian-He Zhao, Yu-Hua Deng, Xian-Tao An, Wen-Dao Chu, Xiang-Zhi Zhang, Chun-An Fan

Summary: Triacylamines with Cs symmetry have been studied in asymmetric organocatalysis, leading to the development of a novel catalytic enantioselective reaction for prochiral triacylamines. This method provides an effective approach for synthesizing chiral imide-esters with a 1,5-dicarbonyl moiety, and has been successfully applied in the asymmetric synthesis of two GABA analogue drugs.

ORGANIC LETTERS (2022)

添加到收藏夹

Article Chemistry, Multidisciplinary

Asymmetric Divergent Synthesis of ent-Kaurane-, ent-Atisane-, ent-Beyerane-, ent-Trachylobane-, and ent-Gibberellane-type Diterpenoids

Xian -He Zhao, Le -Le Meng, Xiao-Tao Liu, Peng-Fei Shu, Cheng Yuan, Xian -Tao An, Tian-Xi Jia, Qi-Qiong Yang, Xiang Zhen, Chun-An Fan

Summary: A unified strategy for asymmetric divergent syntheses of nine C8-ethano-bridged diterpenoids has been developed based on late-stage transformations of common synthons. This strategy allows for the efficient synthesis of these compounds through the regioselective and diastereoselective cyclization reactions of specific functional groups. The successful synthesis of these compounds demonstrates the versatility and reactivity of densely functionalized polycyclic substrates.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2022)

添加到收藏夹

Article Chemistry, Multidisciplinary

Enantioselective Divergent Syntheses of Cephalotaxus Alkaloids: (-)-Cephalotaxine, (-)-Cephalotine B, and (-)-Fortuneicyclidins A and B

Xian-Tao An, Xiao-Min Ge, Xin-Yu Liu, Yu-Han Yang, Xian-He Zhao, Xiao-Yan Ma, Chao Peng, Yi-Jun Fan, Yong Qin, Chun-An Fan

Summary: A new strategy for the asymmetric assembly of the ring D in (-)-cephalotaxine has been developed. This strategy involves a novel Rh-catalyzed annulation reaction for enantioselective construction of the cyclopentane ring D with a spirocyclic aza-quaternary stereocenter. Using this strategy, a concise enantioselective total synthesis of (-)-cephalotaxine has been achieved in nine steps from readily available starting materials. Additionally, the synthesis of related compounds (-)-cephalotine B, (-)-fortuneicyclidin B, and (-)-fortuneicyclidin A has also been accomplished.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

添加到收藏夹

Article Chemistry, Multidisciplinary

Iron(iii)-catalyzed tandem annulation of indolyl-substituted p-quinone methides with ynamides for the synthesis of cyclopenta[b]indoles

Ke-Yin Yu, Xiao-Min Ge, Yi-Jun Fan, Xiao-Tao Liu, Xue Yang, Yu-Han Yang, Xian-He Zhao, Xian-Tao An, Chun-An Fan

Summary: The unique reactivity of indolyl-substituted p-QMs as a new type of two-carbon synthon in a novel iron(iii)-catalyzed tandem annulation has been explored for the first time. The (2+2) annulation/retro-4 pi electrocyclization/imino-Nazarov cyclization cascade reaction is characterized by an unusual structural reconstruction of indolyl-substituted p-QMs, leading to the rapid assembly of synthetically important functionalized cyclopenta[b]indoles.

CHEMICAL COMMUNICATIONS (2022)

添加到收藏夹

暂无数据

© Peeref 2019-2024. All rights reserved.