Article
Chemistry, Organic
Nastassia Varabyeva, Maryia Barysevich, Yauhen Aniskevich, Alaksiej Hurski
Summary: Cyclopropanols, readily available from esters or ketones, undergo diverse ring-opening transformations and can serve as a coupling partner in dual photoredox and nickel-catalyzed reactions. By using the Ti(OiPr)(4) additive, elusive cross-coupling with aryl and alkenyl bromides leading to beta-substituted ketones can be achieved.
Review
Chemistry, Multidisciplinary
Tyler R. McDonald, L. Reginald Mills, Michael S. West, Sophie A. L. Rousseaux
Summary: The carbon-carbon bond cleavage of cyclopropanols is a research hotspot, involving three main reactivity modes such as homoenolate chemistry, beta-keto radical chemistry, and acid-catalyzed ring-opening. Various methods for the C-C bond cleavage and functionalization of cyclopropanols are summarized, emphasizing their synthetic utility.
Article
Chemistry, Physical
Thirupataiah Avullala, Hiep H. Nguyen, Udaya Sree Dakarapu, Parham Asgari, Yuanda Hua, Junha Jeon
Summary: In this study, a method for oxidative C-C activation and silylation of cyclopropanols was reported. By consecutive iridium and rhodium catalysis, α,β-difunctionalized ketones were synthesized with high selectivity.
Article
Chemistry, Organic
Chenhao Lou, Xin Wang, Leiyang Lv, Zhiping Li
Summary: The iron-catalyzed three-component reaction of cyclopropanols with alkenes and tert-butyl hydroperoxide enables the efficient synthesis of 5-oxo peroxides, allowing for the modification of biologically active molecules and various downstream derivatizations.
Article
Chemistry, Organic
Elvira R. Zaitseva, Victoria E. Opryshko, Dmitrii S. Ivanov, Andrey A. Mikhaylov, Alexander Yu. Smirnov, Mikhail S. Baranov
Summary: In this study, it was found that 2-Allyloxybenzaldehydes readily undergo [2 + 1] cycloadditions under 365 nm LED irradiation to form chroman-fused cyclopropanols. This reaction occurs without the need for any catalysts or additives in dimethyl sulfoxide.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Rong-Hua Wang, Zhou Zhang, Bo Li, Gao-Feng Zhu, Jing Shi, Lei Tang
Summary: An intermolecular redox-economical coupling reaction of allyl alcohols with alkynes catalyzed by Ni-Bronsted acid cocatalysis has been developed. This method allows for the synthesis of a diverse range of gamma,delta-unsaturated ketones with high yields and excellent compatibility with various functional groups, demonstrating its significant practical value.
Article
Chemistry, Multidisciplinary
Arup Mondal, Manuel van Gemmeren
Summary: Alkynes are important motifs in organic synthesis due to their presence in natural products and bioactive molecules. The method of inserting alkynes into (hetero)arenes relies heavily on the regioselectivity of the halogenation step, and can achieve selective alkynylation of thiophenes. The developed palladium-catalyzed C-H activation/alkynylation of thiophenes allows for regiodivergent reactions and late-stage modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Kento Tsukiji, Takeru Hayakawa, Kazuya Kanemoto, Naohiko Yoshikai
Summary: In this study, a zinc-mediated annulation reaction between cyclopropanols and alkylidenemalononitriles was reported. The reaction was promoted by Et2Zn and 1,4-diazabicyclo[2.2.2]octane (DABCO) in DMSO at 80 degrees C, resulting in the formation of cyclopropane-fused 6-amino-3,4-dihydro-2H-pyran-5-carbonitrile derivatives with moderate to good yields and high diastereoselectivity. The proposed reaction mechanism involves the generation of an enolized homoenolate as the key reactive intermediate through the ring opening of zinc cyclopropoxide and enolization of the resulting zinc homoenolate, followed by Michael addition, ring closure, and intramolecular cyclization.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Jun-Long Zhan, Lin Zhu, Wei Ren, Bing-Jie Wang, Xin-Ming Zhao, Xin-Ru Zhang, Xin-Yu Zhang, Yao-Qiang Xie
Summary: A feasible and umpolung strategy for synthesizing diverse beta-amino ketones was achieved through TEMPO mediated C-N coupling of cyclopropanols with nitrogen nucleophiles. Mechanism studies showed that enones derived from cyclopropanols are key intermediates and TEMPO plays multiple roles. This protocol offers broad substrate scope, good scalability, and good to excellent yields, providing an alternative approach to the synthesis of structurally important beta-amino ketone scaffolds under metal and additive-free conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Zhijun Zuo, Armido Studer
Summary: In this study, a photoredox-catalyzed 1,3-oxyalkynylation reaction of cyclopropanes with EBXs was described, offering a wide substrate scope.
Article
Chemistry, Organic
Chuan-Ming Hong, Si-Qi Xiong, Xue Zhang, Kai-Xian Ma, Qing-Hua Li, Tang-Lin Liu
Summary: This paper discloses a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)-C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.
Article
Chemistry, Applied
Li-Yun Guo, Qing Li, Yu-Tao Liu, Lin Li, Yu-Qing Ni, Yang Li, Fei Pan
Summary: A palladium-catalyzed method for direct alkynylation of unactivated alkenes via C-H activation, assisted by 8-aminoquinoline, has been successfully developed. This method is applicable to both internal and terminal unactivated alkenes, showing broad functionality tolerance, good regio- and diastereoselectivity, and providing an alternative approach for constructing conjugated 1,3-enynes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Rui Chen, Dengyu Yin, Lishuai Lu, Xiao-Tian Feng, Yandong Dou, Yanwu Zhu, Shilu Fan
Summary: An efficient trifluoromethylalkynylation reaction of gem-difluoroalkenes with alkynyl sulfoxide by photoredox radical addition is developed. This reaction shows good functional group tolerance and moderate to high yields, providing a convenient and cost-effective route for the synthesis of alpha-trifluoromethyl alkynes. The resulting fluorine-containing alkynyl compounds have diverse structural skeletons and are biologically relevant.
Article
Chemistry, Multidisciplinary
Lili Fang, Shuaixin Fan, Weiping Wu, Tielei Li, Jin Zhu
Summary: A low-cost, room temperature ruthenium catalytic method was developed for the synthesis of delta-diketones by coupling alpha-keto sulfoxonium ylides with cyclopropanols. The mild protocol showed a broad substrate scope (47 examples) and high product yield (up to 99%), with mechanistic studies supporting a cyclopropanol ring opening, sulfoxonium ylide-derived carbenoid formation, migratory insertion C-C bond formation pathway.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Ying Xie, Wei Huang, Song Qin, Shaomin Fu, Bo Liu
Summary: An unprecedented intramolecular cascade reaction between alkenes and enones using Fe(acac)(3), PhSiH2(Oi-Pr), and trimethyl borate has been developed to efficiently construct cis-fused bicyclic cyclopropanols, which are commonly found in natural products. This mild protocol features unique regio- and stereo-selectivity and impressive functional group tolerability. Mechanistic studies suggest that the cyclopropane-containing motifs are generated through a stepwise radical process rather than a Michael addition reaction.
ORGANIC CHEMISTRY FRONTIERS
(2021)
