Article
Chemistry, Multidisciplinary
Linlin Ding, Yue Zhao, Hongjian Lu, Zhuangzhi Shi, Minyan Wang
Summary: For the first time, a catalytic enantioselective propargyl-aryl cross-coupling between two electrophiles was achieved in a stereoconvergent manner. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peng Zhang, Qi Xu, Xiao-Mei Wang, Jia Feng, Chuan-Jun Lu, Yingzi Li, Ren-Rong Liu
Summary: The first enantioselective synthesis of N-N bisindole atropisomers via palladium-catalyzed construction of one indole skeleton is reported in this study. A wide variety of N-N axially chiral bisindoles were generated with good yields and excellent enantioselectivities through a cascade condensation/N-arylation reaction. The reaction mechanism and enantiocontrol were further investigated using density functional theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kuai Wang, Jiachang Chen, Wenfeng Liu, Wangqing Kong
Summary: The introduction of fluorine-containing groups into organic molecules can significantly affect their physical and chemical properties and has been widely used in drug discovery and development. In this study, a nickel-catalyzed asymmetric cyclization reaction was described, which enables the efficient synthesis of synthetically attractive 4-fluorovinyl-substituted 2-pyrrolidones. This protocol shows high chemo-, regio-, and enantioselectivities and can be utilized in the synthesis of the antiepileptic drug Seletracetam.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qinglin Zhang, Kang Liang, Chang Guo
Summary: A novel electrolytic system has been introduced to divert standard ionic reactivity, providing a brand-new pattern of reactivity-electricity-driven asymmetric catalysis, which serves as a privileged chiral platform for enantioselective radical allylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Akira Saito, Shinya Adachi, Naoya Kumagai, Masakatsu Shibasaki
Summary: The strategic use of a sterically demanding Ni-II pincer carbene complex has enabled high enantioselectivity in the direct catalytic asymmetric addition of acetonitrile to aldehydes, resulting in highly enantioenriched beta-hydroxynitriles. This highly atom-economical process offers a promising pathway for utilizing inexpensive acetonitrile as a C2 building block in practical synthetic toolbox for asymmetric catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Francesco Calogero, Simone Potenti, Elena Bassan, Andrea Fermi, Andrea Gualandi, Jacopo Monaldi, Busra Dereli, Bholanath Maity, Luigi Cavallo, Paola Ceroni, Pier Giorgio Cozzi
Summary: In this study, a highly enantioselective photoredox allylation of aldehydes was developed using commercially available allyl acetate and chiral nickel complexes as the catalyst. The reaction proceeded under visible-light irradiation at low temperature, providing good to excellent yields and high enantioselectivity. This methodology shows great potential for practical applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dejiang Zhang, Liyuan Le, Renhua Qiu, Wai-Yeung Wong, Nobuaki Kambe
Summary: A strategy for the formation of antimony-carbon bond via nickel-catalyzed cross-coupling of halostibines was developed. This method has a wide substrate scope and is compatible with various functional groups. The successful synthesis of arylated stibine demonstrated the high synthetic potential of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jiaxin Han, Larry Hoteite, Joseph P. A. Harrity
Summary: The first enantioselective Pd-catalyzed asymmetric allylic alkylation of alpha-fluoro-beta-ketoesters has been achieved with up to 92% ee using Trost family chiral ligands. This work provides new insights into the modest selectivities associated with acyclic alpha-fluoroenolates and experimental evidence that poor levels of enantiocontrol in these systems are not necessarily due to E/Z enolate mixtures. Additionally, this methodology enables the easy preparation of useful 3-fluoropiperidine intermediates, demonstrating applicability to a variety of functionalization reactions for the discovery of bioactive products.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Dejiang Zhang, Ting Tang, Zhao Zhang, Liyuan Le, Zhi Xu, Hao Lu, Zhou Tong, Dishu Zeng, Wai-Yeung Wong, Shuang-Feng Yin, Arash Ghaderi, Nobuaki Kambe, Renhua Qiu
Summary: This study presents a general and efficient method for the synthesis of Sb-aryl and Sb-alkyl stibines through nickel-catalyzed cross-coupling reactions with organic halides. The method enables the high selectivity synthesis of complex biaryls and successfully synthesized various molecules, including drugs, with good yields.
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ziqi Zhu, Jieshuai Xiao, Mingjie Li, Zhuangzhi Shi
Summary: This study reports for the first time that chiral nickel complexes can catalyze the intermolecular enantioselective addition of aryl iodides across aldehydes, providing diverse optically active secondary alcohols. The method has a broad substrate scope and mild reaction conditions, avoiding the traditional pre-generation of organometallic reagents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Dominika Kobus-Bartoszewicz, Sebastian Stecko
Summary: We present a convenient two-step method for the synthesis of α-amino ketones through cross-coupling and oxidative cleavage sequence. The cross-coupling reaction enables the functionalization of the molecular platform with aryl/heteroaryl and alkyl groups, while the oxidative cleavage establishes the carbonyl functionality. This strategy offers a versatile approach to access a wide range of α-amino ketones that are not accessible by other methods, making it suitable for various applications in different chemical sciences.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zhilong Li, Leitao Huan, Jian Li, Xiaomin Shu, De Zhong, Wenjing Zhang, Haohua Huo
Summary: In this study, an unprecedented enantioselective cross-electrophile coupling (XEC) of α-amino acid derivatives with aryl bromides was achieved using alcohols as reducing agents via Ni/photoredox catalysis. The method utilizes photocatalytically generated α-hydroxyalkyl radicals to convert alkyl electrophiles to alkyl radicals that can selectively couple with aryl bromides. The scalable protocol allows modular access to valuable enantioenriched benzylic amines and can be applied to late-stage diversification with broad functional group tolerance. Mechanistic studies support the versatility of this alcohol-based reactivity for radical generation and subsequent asymmetric cross-coupling. We expect that this alcohol-based cross-coupling will serve as a general platform for the development of appealing yet challenging enantioselective XECs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Chuan-Jun Lu, Qi Xu, Jia Feng, Ren-Rong Liu
Summary: In the past few decades, the Buchwald-Hartwig reaction has played a vital role in the pharmaceuticals, materials, and catalysis fields as a powerful tool for forming C-N bonds. However, the development of asymmetric Buchwald-Hartwig amination reactions for constructing centered chirality, planar chirality, and axial chirality has been limited due to substrate scope and ligand design challenges. Recent interest in the synthesis of C-N/N-N atropisomers has led to a resurgence in asymmetric Buchwald-Hartwig amination chemistry, providing a practical protocol for the preparation of C-N atropisomers. This review discusses reported protocols and their chemical practicality.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hua-Chen Lin, Gary J. Knox, Colin M. Pearson, Chao Yang, Veronica Carta, Thomas Neil Snaddon
Summary: The biological and therapeutic significance of natural products drives the development of efficient methods for their synthesis. A strategy based on aldol condensation has been developed, which involves direct catalytic alkylation of esters with oxyallenes to regulate the enolate geometry. This strategy shows a broad reaction scope and high levels of stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
