Article
Chemistry, Organic
Xiaoyan Wu, Junjie Fan, Xin Huang, Shengming Ma
Summary: An unexpected rhodium-catalyzed reaction has been reported for the synthesis of specific compounds with high efficiency, showing great potential for further research and applications.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Junjie Fan, Xiaoyan Wu, Chunling Fu, Shengming Ma
Summary: Here we report a Cp*RhCl2-catalyzed three-component coupling cyclization of 2,3-allenoic acids and 2,3-allenols in the presence of Cu(OAc)(2)center dot H2O, resulting in the formation of furanone derivatives. The synthetic potential of this reaction has been demonstrated, and isotopic labeling experiments have revealed unexpected reaction pathways.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Ting-Ting Li, Wen-Ya Lu, Li-Wen Shen, Zhen-Hua Wang, Jian-Qiang Zhao, Yong You, Wei-Cheng Yuan
Summary: A CuI-catalyzed decarboxylative phosphonylation reaction of terminal alkyne-substituted cyclic carbonates/carbamates with phosphine oxides has been developed, resulting in the synthesis of 4-phosphonyl 2,3-allenols and 4-phosphonyl 2,3-allenamines with high regioselectivity. The method demonstrates synthetic utility through large-scale synthesis and versatile transformations of the products.
Article
Chemistry, Multidisciplinary
Marie Deliaval, Ramasamy Jayarajan, Lars Eriksson, Kalman J. Szabo
Summary: We have developed a new three-component catalytic coupling reaction involving alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. This reaction exhibits remarkably high enantio- and diastereoselectivity, leading to the formation of tertiary CF3-allenols with up to three contiguous stereocenters in a single step. The reaction proceeds under mild, neutral, and metal-free conditions, making it highly functional group tolerant.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Guang-Li Xu, Yu-Tong Duan, Zhong-Xia Wang
Summary: In this study, the reaction of 2,3-allenols with PhMe2SiZnCl or Ph2MeSiZnCl under the catalysis of IPrCuCl or SIPrCuCl was carried out, resulting in the formation of 2-silyl-1,3-butadienes. Both secondary and tertiary 2,3-allenols could be used as coupling partners. The reaction of secondary 2,3-allenols exclusively gave (E)-2-silyl-1,3-butadienes as the products.
Article
Chemistry, Organic
Robert Crowley III, Berkley Lujan, Alex Martinez, Roni Manasi, Justin D. Debow, Kevin G. M. Kou
Summary: This article presents a method for manipulating carbon-centered radicals to react with electron-deficient systems. By coupling the Fe(II)-mediated Fenton reaction with the Fe(III)-mediated single-electron oxidation of anisolic compounds, the electron-rich carbon-centered radicals can react with electron-rich arenes, resulting in the production of diarylmethane derivatives from simple unfunctionalized precursors.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yogesh Brijwashi Sharma, Debosmita Das, Murali Mohan Guru
Summary: An efficient route for the synthesis of substituted pyrazolines has been reported using readily accessible N-propargyl hydrazones. The Cu-(II) catalyst acts as a Lewis acid to form an iminium-ion intermediate via cyclization, which upon hydrolysis affords the desired pyrazolines. This methodology has been successfully applied to the synthesis of a progesterone receptor antagonist.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhipeng Zhao, Hongrui Lin, Zheng Zhang, Xiaotong Gao, Congbin Ji, Jian Zhou, Feng Zhou
Summary: In this study, a Cu-catalyzed redox isomerization-reductive deuteration sequence was developed for the synthesis of alpha-deuterated amino acid esters with a Z-configured alkene moiety. The sequence offers mild conditions, broad substrate scope, and excellent stereoselectivity. Additionally, this research presents a rare example of Z-selective redox isomerization of propargyl amines.
Article
Chemistry, Multidisciplinary
Bhaskar B. Dhotare, Sahil Kumar, Amey Wadawale, Sandip K. Nayak, Mukesh Kumar, Dibakar Goswami
Summary: A novel metal-free approach for the synthesis of various 3-substituted-3-arylbenzofuran-2(3H)-ones has been developed via H2SO4-mediated dehydrative substitution, yielding moderate to good yields. Mechanistically, the substitution with the alkoxy group proceeds through a phenolic-hydroxyester intermediate, forming the desired product through cascade dehydration-relactonization steps.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Toshitaka Okamura, Kenta Koyamada, Junichiro Kanazawa, Kazunori Miyamoto, Yoshiharu Iwabuchi, Masanobu Uchiyama, Naoki Kanoh
Summary: This study presents a method for synthesizing difluoropropargyl vinyl ethers from ketones and aldehydes using difluoropropargyl bromide dicobalt complexes, which are then used for the synthesis of various fluorinated compounds under different conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Jiapan Niu, Bowen Liu, Chun Zhang
Summary: A novel and practical method for synthesizing trifluoromethyl tertiary alcohols has been developed. This reaction is compatible with a wide range of functional groups under mild conditions and has demonstrated good potential utility through gram-scale reactions and further transformations. Mechanistic studies have confirmed the radical process of this reaction.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Applied
Geetanjali S. Sontakke, Rahul K. Shukla, Chandra M. R. Volla
Summary: The Rh(I)-catalyzed decarboxylative arylation provides a straightforward platform to access substituted 2,3-allenols and 1,3-butadiene derivatives. The reaction exhibits high regioselectivity and compatibility with various functional groups, allowing the development of a library of diversely functionalized scaffolds with excellent yields. Additionally, late-stage transformation of natural products and downstream transformations highlight the wide applicability and efficacy of the protocol.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Ya-Ping Wang, Xing-Ping Zhang, Ming-Sheng Xie, Hai-Ming Guo
Summary: In this study, highly enantioselective propargyl Claisen rearrangement of O-propargyl beta-ketoesters was achieved using a chiral cobalt complex as the catalyst under mild reaction conditions. A diverse range of chiral allenyl-substituted all-carbon quaternary beta-ketoesters were obtained in good yields and high enantioselectivities.
Article
Chemistry, Organic
Yong-Ze Liu, Yan Jiang, Jun-Lei Zhang, Yan Mei, Dong-Jie Li, Fei Pan
Summary: Bicyclo[1.1.1]pentylketones (BCP ketones) are important bioisosteres of aryl ketones in pharmaceutical chemistry. However, the lack of efficient synthetic methods for BCP ketones hinders early-stage drug discovery. In this study, we developed a photoredox-enabled protocol for the facile synthesis of unsymmetrical 1,3-disubstituted BCP ketones. This method utilizes hypervalent iodine salts and aryl aldehydes to convert [1.1.1]propellane into BCP ketones with moderate to good yields. The reaction is simple, operates at room temperature, and has a broad substrate scope.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Guang-Li Xu, Zhong-Xia Wang
Summary: Regioselective silylation of 2,3-allenols with disilanes was achieved under the catalysis of Pd(2)dba(3)/P(o-MeOC6H4)(3). The presence of Cs2CO3 led to the formation of 2-silyl-1,3-dienes. The reaction showed different selectivities and major isomers depending on the substrate used.
