Article
Chemistry, Organic
Dong-Ping Wu, Wei Ou, Pei-Qiang Huang
Summary: This study describes the catalytic reductive condensation reactions between tertiary amides and active methylene compounds, leading to multifunctionalized non-N-containing products. The reactions proceed through a sequential process involving iridium-catalyzed hydrosilylation of the amides followed by acid-mediated condensation with the active methylene compounds. This scalable method demonstrates a broad scope and remarkable chemoselectivity for the amide group in the presence of various sensitive or even more reactive functionalities such as ester, cyano, nitro, silyl dienol ether, and ketone.
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Jian-Xin Zhang, Bi-Hong Chen, Wei Shu
Summary: This study reports an enantio-selective alkyl-alkyl cross-coupling reaction using a newly-developed chiral tridentate ligand. Two different alkyl halides were successfully cross-coupled to form α-tertiary aliphatic amides. The mechanism investigation revealed that one alkyl halide undergoes oxidative addition with nickel, while the other alkyl halide forms alkyl zinc reagents in situ, enabling reductive alkyl-alkyl cross-coupling without preformation of organometallic reagents.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Wubing Yao, Jiali Wang, Yinpeng Lou, Haijian Wu, Xinxin Qi, Jianguo Yang, Aiguo Zhong
Summary: The study introduced a novel transition-metal-free strategy for chemoselective catalytic reduction of nitro scaffolds to valuable amine functions under mild reaction conditions, which can be readily applied to the preparation of commercially available pharmaceuticals.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Jiahua Chen, Jun Wei Lim, Derek Yiren Ong, Shunsuke Chiba
Summary: The synthesis of alpha-tertiary amines was achieved by iteratively adding carbon nucleophiles to N,N-dialkyl carboxamides, forming anionic tetrahedral carbinolamine intermediates. These intermediates were then treated with bromotrimethylsilane followed by organomagnesium or organolithium reagents to produce alpha-tertiary amines. The use of (trimethylsilyl)methylmagnesium bromide as the second nucleophile allowed for aza-Peterson olefination, resulting in the formation of 1,1-diarylethylenes after acidic work-up.
Article
Chemistry, Organic
Jie Li, Jiaqi Yao, Lingfeng Chen, Dong Zou, Patrick J. Walsh, Guang Liang
Summary: The imide moiety is a well-known structural motif in bioactive compounds and can be utilized as a building block in various processes. A unique feature of the presented method is the use of two different electrophilic acylating reagents, resulting in the formation of unsymmetrical imides with excellent chemoselectivity. Additionally, symmetric imides can be accessed when N-acylglutarimides are used as acylation reagents under similar reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Haipeng Hu, Cuilin Wang, Xin Wu, Yangu Liu, Guizhou Yue, Gehong Su, Juhua Feng
Summary: The catalytic alpha-C-H fluorination of aryl acetic acids was achieved with good functional group tolerance in the presence of a boron catalyst. A series of alpha-fluoro aryl acetic acids were obtained in a single step with high yields (up to 96%). The catalytic reaction was employed for the synthesis of bioactive molecules and the modification of profen drugs.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Sebastian Heindl, Margaux Riomet, Jan Matyasovsky, Miran Lemmerer, Nicolas Malzer, Nuno Maulide
Summary: A chemoselective and robust protocol for the gamma-oxidation of beta,gamma-unsaturated amides has been developed, showcasing the synthetic utility of the products obtained through radical cyclisation reactions and oxidation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Isao Mizota, Yusuke Nakamura, Shunsuke Mizutani, Nanami Mizukoshi, Shunya Terasawa, Makoto Shimizu
Summary: The study demonstrated that alpha-N,N-dialkylaminoamides can be directly synthesized in high yields via an umpolung reaction and rearrangement of dialkylamino groups. Additionally, a short synthesis of a glycine type-1-transporter inhibitor was accomplished with subsequent functional group transformations in 28% overall yield.
Article
Chemistry, Applied
Jiana Hu, Chitturi Bhujanga Rao, Yu Wang, Rui Zhang, Jiacheng Li, Xuebei Ye, Dewen Dong
Summary: A chemoselective cyclodehydration reaction of alpha-acyl-beta-arylaminoacrylamides has been developed using an electrophilic activation strategy. Substituted 4-aminopyridines were selectively prepared in 73-92% yields by activating alpha-acyl-beta-arylaminoacrylamides with hexaphenyloxodiphosphonium triflate (Hendrickson reagent). Substituted diaza[n]phenacenes (n=4-6) were obtained in 72-93% yields directly from alpha-acyl-beta-arylaminoacrylamides using Hendrickson reagent in combination with triflic anhydride (Tf2O). The synthetic protocols have the advantages of readily available starting materials, mild reaction conditions, simple execution, and a wide range of potential products.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yu Wang, Rui Zhang, Jiacheng Li, Chitturi Bhujanga Rao, Xuebei Ye, Dewen Dong
Summary: A facile and efficient method for the synthesis of polysubstituted indoles has been described in this study. The method involves the use of electrophilic activation strategy with either combined Hendrickson reagent and triflic anhydride (Tf2O) or triflic acid (TfOH) to control the chemoselectivity in the intramolecular cyclodehydration. The protocol offers mild reaction conditions, simple execution, high chemoselectivity, excellent yields, and wide range of synthetic potential, making it attractive for academic research and practical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Rajata Kumar Sahoo, Nabin Sarkar, Sharanappa Nembenna
Summary: A new zinc hydride catalyzed partial reduction of heteroallenes via hydroboration, selectively obtaining N-boryl formamide from various isocyanates with different functional groups, indicating potential for chemoselective reduction reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sergio Cuesta-Galisteo, Johannes Schorgenhumer, Xiaofeng Wei, Estibaliz Merino, Cristina Nevado
Summary: This study presents a nickel-catalyzed asymmetric reductive hydroarylation method for synthesizing enantioenriched alpha-arylbenzamides. By using a BIm ligand, diethoxymethylsilane, and aryl halides, aryl groups can be selectively introduced to the internal position of the olefin, creating a new stereogenic center alpha to the N atom with neutral reagents and mild reaction conditions. This provides a straightforward route to pharmacologically relevant motifs found in anticancer drugs, SARS-CoV PLpro inhibitors, and KCNQ channel openers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Biplab Keshari Pandia, Chidambaram Gunanathan
Summary: The unprecedented manganese-catalyzed direct alpha-alkenylation of amides using alcohols was reported, providing alpha,beta-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies showed that the selective olefination is facilitated by metal-ligand cooperation, resulting in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Katreen A. F. Banisalman, Athina Polykandritou, Francis M. Barnieh, Goreti Ribeiro Morais, Robert A. Falconer
Summary: Glycosylation is commonly used to mimic post-translational modifications and modify the properties of peptides. This study introduces a simple and chemoselective method to prepare disulfide-linked glycopeptides. The procedure is highly reactive with cysteine residues in peptides and can be used with unprotected carbohydrates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yiwen Xu, Yang Long, Runyou Ye, Qiang Li, Fang Ke, Xiangge Zhou
Summary: An Fe(III)-catalysed electrochemical method has been developed to transform secondary N-phenyl substituted amides into primary amides. The reaction involves regioselective aryl C-H oxygenation, promoting selective cleavage of the C(phenyl)-N bond and yielding primary amides with up to 92% yield.
Article
Chemistry, Multidisciplinary
Kyan A. D'Angelo, Mark S. Taylor
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2016)
Article
Chemistry, Multidisciplinary
Henry R. Kilgore, Chase R. Olsson, Kyan A. D'Angelo, Mohammad Movassaghi, Ronald T. Raines
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Multidisciplinary Sciences
Kyan A. D'Angelo, Carly K. Schissel, Bradley L. Pentelute, Mohammad Movassaghi
Summary: The study presents a concise total synthesis method for himastatin, a natural product with an unusual homodimeric structure. The final-stage dimerization strategy used in the synthesis was inspired by a detailed understanding of the compound's biogenesis. By combining this approach with a modular synthesis, a series of designed derivatives of himastatin, including synthetic probes to investigate its antibiotic activity, were efficiently accessed.
Article
Chemistry, Multidisciplinary
Kyan A. D'Angelo, Mark S. Taylor
CHEMICAL COMMUNICATIONS
(2017)
