Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Xiu-Qin Dong, Xuanliang Yang, Gang Liu, Xun Xiang, Dezheng Xie, Jinyu Han, Zhengyu Han
Summary: Efficient Ni/(S,S)-Ph-BPE-catalyzed asymmetric hydrogenation of alpha-substituted alpha,beta-unsaturated phosphine oxides/phosphonates/phosphoric acids has been successfully developed, and a wide range of chiral alpha-substituted phosphine hydrogenation products were obtained in generally high yields with excellent enantioselective control (92%-99% yields, 84%->99% ee). This method features a cheap transition metal nickel catalytic system, high functional group tolerance, wide substrate scope generality, and excellent enantioselectivity. A plausible catalytic cycle was proposed for this asymmetric hydrogenation according to the results of deuterium-labeling experiments.
Review
Chemistry, Physical
Srimanta Manna
Summary: Copper-catalyzed enantioselective borylative cyclization is a powerful tool for generating boron-containing carbocycles and heterocycles through the difunctionalization of unsaturated hydrocarbons. This review focuses on the copper-catalyzed borofunctionalization and enantioselective cyclization of alkenes, allenes, and alkynes, as well as the current understanding of the underlying mechanisms.
Article
Chemistry, Multidisciplinary
Liang Tang, Yicong Luo, Cheng Sheng, Fang Xie, Wanbin Zhang
Summary: This article reports the efficient kinetic resolution of gamma-substituted alpha,beta-unsaturated gamma-lactams via a Cu-catalyzed asymmetric boron conjugate addition, which leads to the synthesis of chiral beta-hydroxy-gamma-lactams with beta,gamma-stereogenic carbon centers. The method is successful with a wide range of substrates and exhibits versatile transformations and synthetic utility in biologically active molecules. Mechanistic studies indicate that a Lewis acid Cu-I-catalyzed mechanism is the likely pathway in the catalytic reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chang-Yun Shi, Jungmin Eun, Timothy R. Newhouse, Liang Yin
Summary: A catalytic asymmetric remote conjugate borylation was developed with excellent regioselectivity and high enantioselectivity, leading to the synthesis of versatile chiral compounds in moderate to high yields. Stereomechanistic analysis using DFT calculations provided insights into the origins of regioselectivity. Moreover, the 1,6-borylation reaction was successfully applied in an efficient one-pot asymmetric synthesis of (-)-7,8-dihydrokavain.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Mahadev L. Shegavi, Suresh Saini, Ramesh Bhawar, Meghana Desai Vishwantha, Shubhankar Kumar Bose
Summary: This study reports the anti-Markovnikov-selective hydroboration of alkenes catalyzed by Fe-dopamine-Cu NPs, as well as their application in the beta-borylation of alpha,beta-unsaturated ketones and esters, achieving high yields of alkylboronate esters. Furthermore, the magnetically recyclable catalyst maintained high activity over multiple reaction runs.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Huifang Song, Yuli Sun, Chengrong Lu, Bei Zhao
Summary: Chiral dinuclear rare-earth metal complexes were synthesized and three unknown complexes were characterized. These chiral complexes showed high reactivity in the asymmetric hydrophosphonylation reaction, with complex 7 and chiral diamine proving to be the optimal catalyst combination. The reaction yielded hydrophosphonylation products with high yields and excellent enantiomeric excess values.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Anthony F. Palermo, Bianca Imbriaco, Samantha C. Chan, Brian A. Doan, Sophie A. L. Rousseaux
Summary: In this study, a Cu(I)-catalyzed conjugate borylation of alpha,beta-unsaturated acyl silanes using bis(pinacoloto)diboron was developed. The racemic borylations of beta -aryl-and beta-alkyl-substituted silyl enones were successfully achieved under ligand-free conditions, leading to the synthesis of beta-borylated acyl silanes with high yields. Furthermore, the introduction of Josiphos catalyst enabled the synthesis of enantioenriched boronic esters with improved yields and enantioselectivity. This work demonstrates the scalability of the reaction and shows the ease of isolating the boronic esters using simple separation techniques.
Review
Biochemistry & Molecular Biology
Bingru Li, Huayu Liang, Arumugam Vignesh, Xiaoyu Zhou, Yan Liu, Zhuofeng Ke
Summary: Borylation has emerged as a powerful method for synthesizing organoboranes, which are versatile building blocks in organic synthesis, medicinal chemistry, and materials science. Among various borylation reactions, copper-promoted borylation reactions are highly attractive due to their low cost, non-toxicity, mild reaction conditions, good functional group tolerance, and convenient chiral induction. This review primarily focuses on the recent advances (from 2020 to 2022) in synthetic transformations involving C=C/C equivalent to C multiple bonds and C=E multiple bonds mediated by copper boryl systems.
Article
Chemistry, Multidisciplinary
Nicolas Joly, Alessandro Colella, Monique-Edwige Mendy, Mbaye Diagne Mbaye, Sylvain Gaillard, Albert Poater, Jean-Luc Renaud
Summary: This study reports a visible-light-induced iron-catalyzed alpha-alkylation of ketones using allylic and propargylic alcohols as pro-electrophiles. The diaminocyclopentadienone iron tricarbonyl complex acts as a dual-function catalyst by harvesting light and facilitating dehydrogenation and reduction steps. Under this method, gamma,delta-unsaturated ketones can be synthesized at room temperature through borrowing hydrogen. Steric hindrance on the delta-position of the intermediates plays a key role in preventing or reducing competitive 1,6-reduction and favoring the synthesis of non-conjugated enones and ynones.
Article
Chemistry, Physical
Ryosuke Tsutsumi, Rika Taguchi, Masahiro Yamanaka
Summary: A novel chiral bipyridine ligand with a flexible side chain and molecular recognition site enables precise stereocontrol through the cooperative action of metal center and hydrogen bonds in copper-catalyzed asymmetric borylation. The ligand shows high enantioselectivity in yielding borylated products, with potential to control chemo- and site selectivity in addition to stereoselectivity.
Article
Chemistry, Applied
Roman Ottenbacher, Vladimir Kurganskiy, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: In this study, we reported the enantioselective epoxidation of electron-deficient cis- and trans-alpha,beta-unsaturated amides using the environmentally benign oxidant H2O2. The manganese complexes with bis-amino-bis-pyridine and related ligands as catalysts showed high efficiency and excellent chemo- and enantioselectivity. The presence of NH moiety was found to enhance the enantioselectivity and yield of cis-enamides epoxidation significantly.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Koji Kubota, Daiyo Miura, Takumi Takeuchi, Shun Osaki, Hajime Ito
Summary: The study introduces a novel catalytic enantioselective nucleophilic borylation reaction of ketimines, leading to the efficient synthesis of optically active alpha-amino tertiary boronates with high enantioselectivity. The products can be further converted into peptidylboronic acid derivatives that are difficult to synthesize by other methods. Density functional theory calculations suggest that noncovalent interactions play a crucial role in determining the enantioselectivity of this reaction.
Article
Chemistry, Multidisciplinary
Hui-Qing Geng, Xiao-Feng Wu
Summary: In this study, we have developed a copper-catalyzed hydroaminocarbonylation of benzylidenecyclopropanes under relatively mild conditions. A series of gamma,delta-unsaturated amides with a broad range of functional groups were obtained in moderate to good yields. Both dialkyl-substituted and monoalkyl-substituted hydroxylamine derivatives can be applied in this transformation to give the corresponding tertiary and secondary amides successfully.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Xinhua Duan, Pengfei Li
Summary: The study presented a mild, rapid copper-catalyzed diborylation reaction for the synthesis of stereodefined multifunctionalized beta,gamma-unsaturated ketones. Fine control of chemo-, regio-, Z/E and diastereoselectivity was achieved, expanding the substrate scope and proposing a possible catalytic cycle to explain the selectivity.
CHINESE JOURNAL OF CHEMISTRY
(2021)
