Article
Chemistry, Physical
Xiao-Qing Han, Lei Wang, Ping Yang, Jing-Yuan Liu, Wei-Yan Xu, Chao Zheng, Ren-Xiao Liang, Shu-Li You, Junliang Zhang, Yi-Xia Jia
Summary: A palladium-catalyzed intramolecular enantioselective Mizoroki-Heck reaction of naphthalenes has been developed, leading to the formation of a series of unique heterocyclic compounds with enantiomeric excess values retained. The reaction relies on the use of a chiral sulfonamide phosphine ligand to inhibit competitive and undesired reactions.
Article
Chemistry, Multidisciplinary
Dong Gao, Lei Jiao
Summary: This study presents an efficient method for constructing indoline structures with a C2-quaternary stereocenter and controlling the migrating group through aza-semipinacol rearrangement. It enables the divergent access to dearomatized indole derivatives with either a C3- or a C2-quaternary stereocenter.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Logan E. Vine, Ryan D. Reeves, Eleanor M. Landwehr, Israel Fernandez, Jennifer M. Schomaker
Summary: This study demonstrates predictable control over the mechanism of Pd-catalyzed allene cross-coupling/cyclization and cycloisomerization by targeted changes to the reaction conditions, resulting in the successful access to enantioenriched cyclopropanes and cyclopentenes. Furthermore, it shows a simple switch of the ligand on Pd can divert the reactivity of allenyl malonate from cross-coupling/cyclization to cycloisomerization.
Article
Chemistry, Multidisciplinary
Esteban Matador, Javier Iglesias-Siguenza, David Monge, Pedro Merino, Rosario Fernandez, Jose M. Lassaletta
Summary: A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines has been developed using N-tert-butylhydrazones as key neutral reagents, leading to the formation of appealing dihydroisoquinoline derivatives with excellent stereocontrol. Experimental and computational data support the generation of highly ordered complexes that play a crucial role in the selective and high-yielding transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mukesh Pappoppula, Kathryn L. Olsen, Devin R. Ketelboeter, Aaron Aponick
Summary: A highly enantioselective alkynylation of pyridine is reported. The reaction is enabled by StackPhos and proceeds with excellent regioselectivity (25 : 1), enantioselectivity (up to 99 % ee), and yield (up to 99 %). Terminal alkynes with a wide range of functional groups work well in the transformation, including acetylene gas, paving the way for the use of these feedstock starting materials to rapidly access highly useful synthetic intermediates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Qian Wan, Jia-Hao Xie, Chao Zheng, Yao-Feng Yuan, Shu-Li You
Summary: In this study, a catalytic asymmetric dearomatization reaction of electron-deficient heteroarenes with alpha-substituted isocyanoacetates was reported, leading to a range of optically active pyrrolo[3,4-b]indole derivatives. The reaction yielded good results with high stereoselectivities, using a catalytic system consisting of a cinchona-derived amino-phosphine and silver oxide. This method features wide substrate scope, mild conditions, and provides a new strategy for developing asymmetric dearomatization reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Claire Segovia, Pierre-Antoine Nocquet, Vincent Levacher, Jean-Francois Briere, Sylvain Oudeyer
Summary: This review summarizes the achievements in the field of organocatalyzed nucleophilic dearomatization of azaarenium salts, highlighting the versatility of the approach through classification of different activation modes and discussion of chemical transformations of the resulting products.
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jian-Hua Liu, Qing Zhou, Yao Lin, Zhu-Lian Wu, Tian Cai, Wei Wen, Yan-Min Huang, Qi-Xiang Guo
Summary: In this study, a highly efficient atom-economic asymmetric alpha-allylation method using chiral-aldehyde/palladium catalyst was reported. This method enables the asymmetric alpha-allylation of different 1,3-dienes and allenes with N-unprotected amino acid esters, leading to the synthesis of alpha,alpha-disubstituted chiral alpha-amino acid esters with high efficiency, good yields, and stereoselectivities. No N-allylation byproducts were observed in these reactions. Two reaction models were proposed based on mechanistic control experiments. Overall, this work demonstrates a new approach for preparing structurally diverse chiral amino acids and provides insights for developing chiral-aldehyde catalytic systems.
Article
Chemistry, Applied
Linhong Zuo, Wusheng Guo
Summary: A Pd-catalyzed decarboxylative approach for the construction of 2-allyl-2,2-diarylacetaldehydes via a dearomative umpolung strategy is presented. The reaction is applicable to various cyclic carbonates or allylic acetates with different functional groups. The reaction can be scaled up to gram-scale without loss of efficiency. Control experiments suggest that the reaction proceeds through a palladium-catalyzed dearomative decarboxylation step followed by an umpolung nucleophilic attack.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Riccardo Pedrazzani, Juzeng An, Magda Monari, Marco Bandini
Summary: New chiral BINOL-based phosphate counterions have been synthesized and utilized in the gold-catalyzed enantioselective dearomatization reaction, leading to a range of densely functionalized C1-allylated naphthalenones with high levels of chemo-, regio-, and stereoselectivity (up to 95% ee).
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Nicola Camedda, Franca Bigi, Raimondo Maggi, Giovanni Maestri
Summary: A sequential strategy enables the challenging assembly of dihydronaphthalenes through the key annulation of an alkyne with a vinylarene under mild conditions. The products are obtained in good yields and exhibit high functional tolerance, thanks to the domino nucleophilic substitution and dearomative Diels-Alder and ene reactions. DFT modeling data suggest that alkali cations play a crucial role in ensuring a smooth dearomative cyclization of the in situ generated intermediates.
Article
Chemistry, Organic
Christopher W. Davis, Tanner W. Bingham, Mikiko Okumura, David Sarlah
Summary: This study presents a palladium-catalyzed, dearomative syn -1,2-diamination of non-activated arenes benzene and naphthalene using aryl isocyanates, offering a unique synthetic pathway with complementary regio- and stereoselectivity. The products obtained are amenable to further synthetic elaboration, allowing for selective diene functionalization and heterocycle cleavage. Overall, this dearomatization process provides access to novel saturated nitrogen-containing heterocyclic motifs and syn -1,2-diaminated cyclohexane products.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Kai Liu, Yu-Feng Song, Yang Gao, Jie-Qiong Luo, Yi-Xia Jia
Summary: A NiH-catalyzed intermolecular dearomative hydroalkylation of indoles has been developed to efficiently synthesize a diverse array of C2-alkylated indolines. This protocol exhibits good functional group tolerance and can be used for late-stage functionalization of complex drug molecules.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)