Article
Chemistry, Organic
Cai-Yan Zhang, Ke Cao, Han-Bo Yang, Li-Fang Ding, Junxiao Yang
Summary: The Cu(OTf)(2)/NBS-mediated tandem reaction of 1-cinnamyl alcohol-o-carboranes for the synthesis of C-alkenyl-o-carboranes has been developed. Mechanism studies revealed that the ring opening of oxetane with electron-rich arenes as nucleophiles, promoted by Cu(OTf)(2), was the key step for the transformation. This work provides an alternative strategy for the synthesis of C-alkenyl-o-carboranes, which has important implications for diversifying o-carborane derivatives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mengna Zhao, Qian Miao
Summary: The B3N6-[4]triangulene, a key structural unit of BC4N, was successfully synthesized through nitrogen-directed borylation, showing hydrogen-bonding properties. Its slightly bent triangular polycyclic framework consists of 4 pi-electron N-B-N units and forms hydrogen bonds with other molecules like halide or carboxylate anions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sebastian Mummel, Felix Lederle, Eike G. Huebner, Jan C. Namyslo, Martin Nieger, Andreas Schmidt
Summary: Sydnone methides are rare compounds that can form pi-electron rich anionic N-heterocyclic carbenes and coordinate with various metals, while also undergoing C-C coupling reactions under specific catalysts. Studies have determined their electronic properties and NMR spectra.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shengjun Ni, Matic Hribersek, Swarna K. Baddigam, Fredric J. L. Ingner, Andreas Orthaber, Paul J. Gates, Lukasz T. Pilarski
Summary: This new mechanochemical method enables highly regioselective C-H methylation of (hetero)arenes, showing excellent functional-group compatibility and shorter reaction times, and can be used for the synthesis of biologically active compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Kezhuo Zhang, Chenchen Li, Yining Jia, Wanxiang Zhao
Summary: This study presents a novel strategy for the preparation of gamma-lactones through the oxidation of enynyl boronates. By oxidizing the C(sp)-B bond and subsequently performing epoxidation and lactonization, various gamma-lactones and unsaturated butenolides can be efficiently synthesized. Furthermore, asymmetric oxidative lactonization of enynyl boronates can generate chiral gamma-lactones with high enantioselectivities and diastereoselectivities. The versatile transformations and prevalence of gamma-lactones highlight the importance of this strategy in the construction and late-stage functionalization of complex molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhenyu Li, Xuan Ai, Hui Chen, Xiao Liang, Xiaotian Li, Dong Wang, Xiaoxin Zou
Summary: Intermetallic rhodium boride (RhB) is synthesized with an asymmetrically strained hcp Rh sublattice, in which the covalent interaction of interstitial boron atoms is identified as the main contributor. Additionally, RhB is recognized as a hydrogen-evolving electrocatalyst with Pt-like activity, attributed to the optimized electronic structure induced by Rh(d)-B(s,p) orbital hybridization.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Andrew J. Vetter, Tarah A. DiBenedetto, Mikhaila D. Ritz, William D. Jones
Summary: The catalytic C-H activation and borylation of arenes by trispyrazolylborate complexes have been successfully demonstrated using ethylene complexes Tp'Rh(C2H4)(2) and Tp'Ir(C2H4)(2).
Article
Chemistry, Multidisciplinary
Xinxin Tang, Raj K. Tak, Hidetoshi Noda, Masakatsu Shibasaki
Summary: We report the stereoselective synthesis of remotely decorated, trisubstituted beta-prolines via Rh-catalyzed C-H amination. The method works well in the presence of various functionalities, with carboxylic acids in the products serving as gateways for diverse downstream transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yanhui Chen, Si Wen, Qingyu Tian, Yuqing Zhang, Guolin Cheng
Summary: This study presents a direct C(sp)-, C(sp(2))-, and C(sp(3))-H thiolation reaction using beta-sulfinylesters as the sulfur source. The chemoselective C-S bond cleavage of sulfonium salts formed in situ from alkenes, alkynes, and 1,3-dicarboxyl compounds with beta-sulfinylesters was successfully demonstrated, supporting a retro-Michael reaction mechanism.
Article
Chemistry, Applied
Takeshi Yasui, Yuya Nakazato, Koutarou Kurisaki, Yoshihiko Yamamoto
Summary: In this study, a Rh-catalyzed asymmetric [2+2+2] cycloaddition reaction was reported, resulting in the synthesis of enantio-enriched tricyclic cyclohexadienes with a quaternary bridgehead carbon. It was found that the Rh-Phanephos complex was the most suitable catalyst, while Rh-biaryl bisphosphine catalysts were not applicable.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Max Wienhold, John J. Molloy, Constantin G. Daniliuc, Ryan Gilmour
Summary: Modular beta-borylacrylates have been shown to play a crucial role in generating diverse coumarins, with the BPin unit enabling the cascade annulation of 2-halo-phenol derivatives. Mild isomerisation allows for the synthesis of structurally varied coumarins, and the method has potential applications in bioassay development and drug repurposing.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Hui Sun, Yi Cheng, Houyun Teng, Xiaoqi Chen, Xiaokang Niu, Hao Yang, Yu-Ming Cui, Li-Wen Xu, Lei Yang
Summary: An iridium-catalyzed, directing group-enabled site selective intra- and intermolecular silylation of indoles and pyrroles with hydrosilanes has been developed under ligand-free conditions. Fine-tuning of the removable 3-alkyl-2-pyridyl directing group was crucial for achieving high yields for C2-silylated indole and pyrrole products. Scalability and further transformations of the silylation products have also been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Stephan Hagspiel, Felipe Fantuzzi, Rian D. Dewhurst, Annalena Gaertner, Felix Lindl, Anna Lamprecht, Holger Braunschweig
Summary: Lewis base adducts and cyclodimers of the parent boraphosphaketene were prepared for the first time, with one adduct undergoing decarbonylation and phosphinidene insertion to form very rare 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines were confirmed through synthesis of their pi complexes with Group 6 metals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Papiya Sikdar, Tathagata Choudhuri, Suvam Paul, Sourav Das, Avik Kumar Bagdi
Summary: A one-pot methodology has been developed for the synthesis of 3-halo-pyrazolo[1,5-a]pyrimidine derivatives through a three-component reaction. The reaction utilizes easily accessible 1,3-biselectrophilic reagents, offering a straightforward approach for the synthesis of these compounds. The reaction conditions are mild, environmentally benign, and show wide functional group tolerance.
Article
Chemistry, Organic
Tobias Krueger, Andrea Bramborg, Alexandra Kelling, Eric Sperlich, Torsten Linker
Summary: A convenient method for the synthesis of gamma-spirolactones in only 2-3 steps has been described, resulting in more than 30 new compounds. The process involves Birch reduction of aromatic carboxylic acids followed by direct lactonization, and subsequent hydrogenation with Pd/C catalyst. The method allows for the construction of up to 3 new stereogenic centers from achiral benzoic acids.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Chang Wang, Peng-Cheng Qian, Fan Chen, Jiang Cheng
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Organic
Gang Wang, Jin-Chen Li, Yong-Gui Zhou, Zhi-Shi Ye
Summary: This paper presents an enantioselective construction method for indole-fused bicyclo[3.2.1]octanes, utilizing a Heck-type reaction triggered by aminopalladition to achieve construction of an all-carbon quaternary bridgehead stereocenter, with mild conditions and good tolerance for various functional groups. The method can be scaled up to demonstrate practicality.
Article
Chemistry, Organic
Kui Liu, Shao-Jie Cheng, Gen Luo, Zhi-Shi Ye
Summary: A new and facile method for the synthesis of 1-substituted cyclopropylamines via phosphine-catalyzed reaction was described. It shows good selectivity and efficiency, and practicality for late-stage modification, scaled-up reactions, and formal synthesis. Mechanistic aspects were elucidated through experimental and computational studies.
Article
Chemistry, Organic
Shao-Jie Cheng, Gang Wang, Kui Liu, Zhi-Shi Ye
Summary: A palladium-catalyzed regioselective alpha-amino C-H functionalization has been established via the isomerization of alpha,beta-unsaturated carbonyls including esters, ketones, and amides, providing a straightforward access to a wide range of multicyclic compounds with good yields. This transformation exhibits high regioselectivity, excellent functional group tolerance, and scalability.
Review
Chemistry, Organic
Zhi-Shi Ye, Jin-Chen Li, Gang Wang
Summary: In this concise review, we summarize the transition metal-catalyzed enantioselective synthesis methods of indoles from 2-alkynyl-anilines.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Organic
Kui Liu, Gang Wang, Zhe-Wen Zhang, Yu-Yang Shi, Zhi-Shi Ye
Summary: This study documents an effective strategy for the ring-opening/elaboration of cyclopropanes using a phosphine catalyst, which produces 2,4-pentadiene sulfonamides and isoindolines in moderate to good yields. The key to the success of this reaction lies in the phosphine-catalyzed introduction of a trigonal center into cyclopropanes, resulting in the formation of a higher ring strain cyclopropylidenemethyl phosphonium salt. Furthermore, this methodology is utilized as a crucial step in the synthesis of bioactive molecules.
Article
Chemistry, Organic
Fei-Ruo Zhang, Fanshu Cao, Kui Liu, Yi-Ping He, Gen Luo, Zhi-Shi Ye
Summary: A chiral Lewis base catalyzed enantioselective N-allylic alkylation reaction of 2-hydroxypyridines has been documented, leading to the convenient synthesis of N-alkylated 2-pyridones with high enantioselectivity and yield. Experimental and computational studies reveal that the strong hydrogen bond interaction between the chiral Lewis base catalyst and 2-hydroxypyridines is crucial for the reactivity, chemoselectivity, and enantioselectivity of this reaction.
Article
Chemistry, Organic
Chen Liang, Zhibin Chen, Xinyue Hu, Shengxia Yu, Zhenlian Wang, Jiang Cheng
Summary: We developed a phosphine-catalyzed ring-opening reaction of cyclopropenones with dicarbonyl compounds as C-nucleophiles, leading to 1,3,3'-tricarbonyl compounds. This transition-metal free procedure features mild and neutral reaction conditions with good atom economy, providing an easy pathway to access 1,3,3'-tricarbonyl derivatives.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xi Yang, Gang Wang, Zhi-Shi Ye
Summary: In this study, a novel and efficient palladium-catalyzed reaction was disclosed for the simultaneous construction of heteroaromatic ring and methyl group, resulting in moderate to excellent yields. This methodology played a key role in the synthesis of pregnane X receptor antagonists.
Review
Chemistry, Organic
Lu Wang, Ying Shao, Jiang Cheng
Summary: The cyanation reaction plays a key role in organic chemistry due to the wide applications of nitrile compounds. Traditionally, metal cyanides were used as cyanide sources, but recent research shows the potential of using combined cyanide sources for cyanation reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Shengnan Jin, Fan Chen, Pengcheng Qian, Jiang Cheng
Summary: A new method using DTBP as a promoter allows for the difunctionalization of alpha-aryl alpha-alkynyl allylic alcohols with alkyl nitriles, resulting in alpha-alkynyl gamma-cyano functionalized ketones. This process involves C(sp(3))-H bond cleavage of alkyl nitriles and radical 3-exo-dig cyclization, with a preference for 1,2-alkynyl migration over 1,2-aryl migration.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Organic
Chang Wang, Fan Chen, Pengcheng Qian, Jiang Cheng
Summary: The Rh-catalyzed C-H bond activation/annulation provides a new strategy for the synthesis of new frameworks, with important research significance and application prospects.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chang Wang, Xiaodong Fan, Fan Chen, Peng-Cheng Qian, Jiang Cheng
Summary: A rhodium-catalyzed annulation of vinylene carbonate with amidines was developed in this paper, leading to 4-methylquinazolines with moderate to excellent yields. The procedure proceeded by sequential ortho-acylation and annulation, utilizing vinylene carbonate as the acetylation reagent.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Zhixin Wang, Yang Li, Fan Chen, Peng-Cheng Qian, Jiang Cheng
Summary: A Bronsted acid-promoted intramolecular cyclization reaction was developed in the presence of TsNHNH2 to synthesize polysubstituted indenes with complexity and diversity. Unlike other reactions, a cationic cyclization pathway was involved in this method, where N-tosylhydrazone served as an electrophile and alkylation reagent.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Shao-Jie Cheng, Gang Wang, Kui Liu, Zhi-Shi Ye
Summary: A palladium-catalyzed regioselective alpha-amino C-H functionalization via the isomerization of alpha,beta-unsaturated carbonyls has been established, providing access to a wide array of tricyclic compounds in good yields. This transformation shows high regioselectivity, excellent functional group tolerance, and scalability, and has been used as a key step in the total synthesis of natural products. Preliminary mechanistic studies suggest that the palladium catalyst not only promotes the isomerization of unsaturated carbonyls but also plays a role in the final protonation/cyclization.
