Article
Chemistry, Organic
Jianguo Yang, Saimei Liu, Peng Hong, Jinshan Li, Zhiming Wang, Jun Ren
Summary: A novel and efficient synthesis method for structurally diverse 2,2-difluoro-3-hydroxy-1,4-diketone derivatives is described, using readily available glyoxal monohydrates and difluoroenox-ysilanes. This method utilizes the distinctive fluorine effect of the reactants and the fluoroalcohol catalyst, representing the first application of fluoroalcohol catalysis in a Mukaiyama aldol reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Natalie C. Dwulet, Vincenzo Ramella, Christopher D. Vanderwal
Summary: Soft enolization conditions are shown to be more efficient than hard enolization protocols in regioselectively forming enoxysilanes from unsymmetrical 3-substituted cycloalkanones. The regioselectivities achieved are complementary to those obtained from cycloalkenone conjugate addition/enolate silylation with high selectivity.
Article
Chemistry, Organic
Kwihwan Kobayashi, Shingo Komatsuzaki, Shun-ya Onozawa, Koichiro Masuda, Shu Kobayashi
Summary: We present a green method for the synthesis of aryl enol ethers from phenols and dimethyl ketals using aluminium as a catalyst, without halides and transition metals. The ketal exchange reaction is driven by the removal of methanol. The obtained aryl enol ethers can be transformed into diaryl ethers through Pd/C-catalysed dehydrogenation or DDQ oxidation. This method is significant for the synthesis of important intermediates or building blocks in organic synthesis and polymer chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Kwihwan Kobayashi, Shingo Komatsuzaki, Shun-ya Onozawa, Koichiro Masuda, Shu Kobayashi
Summary: We present an aluminium-catalysed, halide- and transition metal-free method for synthesizing aryl enol ethers from phenols and dimethyl ketals through ketal exchange driven by methanol removal. The obtained aryl enol ethers can be further transformed into diaryl ethers using Pd/C-catalysed dehydrogenation or DDQ oxidation. This new protocol provides a halide- and transition metal-free approach for the synthesis of phenols and dimethyl ketals, which are important intermediates or building blocks in organic synthesis and polymer chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Jian-Yu Zou, Yu-Zhao Wang, Wen-Hui Sun, Wu-Jie Lin, Xue-Yuan Liu
Summary: A mild and facile approach has been developed to construct various perfluoroketones via photo-catalyzed difluoroalkylation of difluoroenoxysilanes. The reaction involves a strategy of combining two fluorine-containing functional groups, allowing for high efficiency, mild conditions, and broad scope. Various fluoroalkyl halides can be utilized as radical precursors, suggesting a potential single-electron transfer pathway in the reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sophi R. Todtz, Cory W. Schneider, Tanmay Malakar, Clare Anderson, Heather Koska, Paul M. Zimmerman, James J. Devery
Summary: Lewis acid-catalyzed carbonyl-olefin metathesis has revealed new behaviors of Lewis acids, particularly the solution behaviors of FeCl3. Adding TMSCl to FeCl3-catalyzed carbonyl-olefin metathesis leads to significant deviations from normal reactivity, mitigating byproduct inhibition and increasing the reaction rate. Quantum chemical simulations suggest the formation of a silylium catalyst that binds to carbonyl groups, with potential utility in carbonyl-based transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Xi-Yu Wang, Min Yang, Ying Zhou, Jian Zhou, Yong-Jia Hao
Summary: A highly efficient metal-free selective 1,4-addition reaction of difluoroenoxysilanes to chromones was developed using HOTf as the catalyst, providing a facile method to access valuable C2-difluoroalkylated chroman-4-one derivatives. The products could be converted to the difluorinated bioisostere of the natural product (S)-2,6-dimethylchroman-4-one and a difluorinated benzo-seven-membered heterocycle via the Schmidt rearrangement reaction. Compound 3g exhibited potent inhibitory effect on HCT116 cancer cells, making it a promising lead compound for further optimization and evaluation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Yang Shi, Bo-Wen Pan, Jun-Xiong He, Ying Zhou, Jian Zhou, Jin-Sheng Yu
Summary: The O-site reactivity of difluoroenoxysilanes has been reported for the first time, allowing for the direct construction of versatile gem-difluoroalkenes through an highly efficient addition reaction with ketenes. A series of valuable gem-difluoroenol esters were synthesized in good to excellent yields, showcasing the synthetic versatility of this method through gram-scale synthesis and good functional group tolerance.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Subba Rao Polimera, Murugaiah A. M. Subbaiah, Andivelu Ilangovan
Summary: A regioselective 1,2-addition of silyl enol ethers to quinones can now be achieved via a palladium(II) enolate pathway, providing access to cyclohexadienone derivatives. This protocol proceeds under mild reaction conditions without the need for an external ligand or base, and the products have been used as synthetic precursors for fused heteroaryl systems.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xuening Li, Ying Li, Yuanyuan Sun, Lingpeng Meng, Yanli Zeng
Summary: The mechanism of the Mukaiyama aldol reaction was investigated using density functional theory, revealing that BF3 serves as a good catalyst for the reaction by lowering the energy barrier of the carbon-carbon bond formation process. The tension between different ring structures and the charge transfer in acetaldehyde may contribute to the catalytic effect of BF3.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Peter-Yong Wang, Itai Massad, Ilan Marek
Summary: The facile and modular access to stereodefined disubstituted aldehyde-derived silyl enol ethers allowed for their successful application in a stereoselective aldol reaction, resulting in excellent yields and diastereomeric ratios. The counter-intuitive stereochemical behavior of this Mukaiyama-aldol reaction is explained by a non-classical open transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Masahito Yoshida, Yuhi Okoshi, Hideo Kigoshi
Summary: A concise total synthesis of metacridamides A and B was achieved through repetitive vinylogous Mukaiyama aldol reactions and ynamide-mediated macrolactonization. The spectral data of the synthetic products matched those of the natural compounds, leading to the reassessment of the absolute configuration of the C-9 position as S.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhibing Weng, Ying Zhou, Xin Yue, Feng Jiang, Wengang Guo
Summary: In this study, catalytic asymmetric alpha-regioselective Michael additions of vinylogous alpha-ketoester enolates were conducted efficiently using a chiral bifunctional organocatalyst. The reactions yielded Rauhut-Currier type products with high yields and excellent regio- and enantioselectivities.
Article
Biochemistry & Molecular Biology
Michel Grosse, Kerstin Guenther, Paul M. Jordan, David Roman, Oliver Werz, Christine Beemelmanns
Summary: This study describes the synthesis of delta-hydroxy-beta-keto esters and their evaluation for anti-inflammatory properties. The products exhibited excellent enantioselectivities and surprising structure-activity relationship.
Article
Chemistry, Organic
Yu-Liang Pan, Ying-Bo Shao, Zhen Liu, Han-Liang Zheng, Liu Cai, Hai-Chang Zhang, Xin Li
Summary: A practical and efficient method for the asymmetric difluorocarbonylation reaction of non-active imines with difluoroenoxysilane has been reported, yielding products with high efficiency and enantioselectivity. The method can also be applied to other compounds and the synthetic utility of the products has been demonstrated through diverse transformations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Fu-Min Liao, Yun-Lin Liu, Jin-Sheng Yu, Feng Zhou, Jian Zhou
ORGANIC & BIOMOLECULAR CHEMISTRY
(2015)
Article
Chemistry, Multidisciplinary
Liao Fumin, Du Yi, Zhou Feng, Zhou Jian
ACTA CHIMICA SINICA
(2018)
Review
Chemistry, Organic
Fumin Liao, Jinsheng Yu, Jian Zhou
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2017)
Review
Chemistry, Multidisciplinary
Fu-Min Liao, Zhong-Yan Cao, Jin-Sheng Yu, Jian Zhou
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2017)
