Article
Chemistry, Organic
Jia-Yin Wang, Guigen Li, Wen-Juan Hao, Bo Jiang
Summary: A new asymmetric catalytic conjugate reduction method has been established for synthesizing enantioenriched cyclobuta[a]-naphthalen-4(2H)-ones using copper-bisphosphine complexes as catalysts, providing excellent regio- and enantioselectivities. This protocol is tolerant to a broad scope of substrates, exhibits high compatibility with various substituents, and offers excellent stereoselectivity.
Article
Chemistry, Organic
Gillian Laidlaw, Vilius Franckevicius
Summary: A palladium-catalyzed decarboxylative asymmetric allylic alkylation has been developed for the synthesis of specific compounds, demonstrating potential for medicinal chemistry applications.
Article
Chemistry, Organic
Vaibhav B. Patil, Sandip B. Jadhav, Jagadeesh Babu Nanubolu, Rambabu Chegondi
Summary: In this study, a CuH-catalyzed asymmetric desymmetrization reaction of prochiral cyclopentane-1,3-diones was reported. By using PMHS as a cost-effective hydride source, cyclic 3-hydroxy ketones with an all-carbon quaternary center could be synthesized with high diastereoselectivity. The reaction demonstrated excellent functional group tolerance, including reducible alkyne, alkene, and ester groups, and showed a broad substrate scope. The importance of chiral cyclic 3-hydroxy ketone building blocks was further demonstrated through the synthesis of (-)-estrone, the toxicodenane E core, and fused indoles.
Article
Chemistry, Organic
Zhifang Chen, Yufeng Zhou, Tingjun Hu, Heng-Ying Xiong, Guangwu Zhang
Summary: This unprecedented 1,3-dipole cycloaddition between acyclic CF3-ketimines and N-benzyl azomethine ylide has been enabled by tungsten catalysis, leading to a range of novel imidazolidines with a trifluoromethylated tetrasubstituted carbon center. The gram-scale synthesis capability and variant derivatizations of cycloaddition adducts demonstrate the synthetic potential of this approach, providing easy access to a rapidly expanding library of motifs with a trifluoromethylated fully substituted carbon.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Manman Kong, Yaqi Tan, Xiaowei Zhao, Baokun Qiao, Choon-Hong Tan, Shanshan Cao, Zhiyong Jiang
Summary: A novel enantioselective protonation protocol triggered by reductive cross coupling of olefins was reported. This method allows for the synthesis of important enantioenriched azaarene derivatives with tertiary stereocenters at their remote delta-position with high yields and enantioselectivities, showcasing its significant synthetic value.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Cheng-En Hsieh, Chih-Yao Tsao, Cheng-Huan Chuang, Liang-Wei Chen, Chih-Ming Chou
Summary: A palladium-catalyzed regiospecific decarboxylative epsilon-allylation of (cyclohexadienylidene)malononitriles was developed for the synthesis of functionalized alpha-allyl-alpha-aryl malononitriles, resulting in a wide range of products with high yields and excellent linear selectivity. The resulting products can be further transformed into valuable synthetic intermediates through decyanation and Mizoroki-Heck arylation. Additionally, an enantioselective decarboxylative allylation reaction was also demonstrated in the study.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Steven M. Wales, Rakesh K. Saunthwal, Jonathan Clayden
Summary: This paper summarizes the research on the asymmetric synthesis of heavily substituted benzylic stereogenic centers and describes a series of new reactions and mechanistic studies. A new method for enantiospecific arylation at benzylic stereogenic centers in organolithium intermediates was discovered. Experimental and computational studies confirmed a low kinetic barrier and conformational guiding factors, enabling the high tolerance and reaction rate. Similar reactions with other anilide-based functional groups were also discovered and the application scope was expanded.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Multidisciplinary Sciences
Chenhuan Zhang, Xianqing Wu, Tingting Xia, Jingping Qu, Yifeng Chen
Summary: Nitrogen-based heterocycles, particularly enantioenriched lactams, are widely present in pharmaceuticals. Despite extensive efforts, a method for synthesizing delta-lactams remains elusive. In this study, a Ni-catalyzed enantioselective carbamoylation was developed to efficiently access two types of common six-membered lactams. The newly developed chiral 8-Quinox skeleton ligand played a crucial role in enhancing reactivity and enantioselectivity.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Lingfei Hu, Han Gao, Yanlei Hu, Yan-Bo Wu, Xiangying Lv, Gang Lu
Summary: The factors controlling the regioselectivity in alkene hydrocupration were investigated computationally using energy decomposition analysis. It was found that the Markovnikov-selective hydrocupration with electronically activated mono-substituted olefins is mainly influenced by destabilizing Pauli repulsion due to the electron delocalization effect. On the other hand, the anti-Markovnikov-selective hydrocupration with 1,1-dialkyl-substituted terminal olefins is dominated by repulsive electrostatic interactions caused by the unequal pi electron distribution induced by alkyl substituents.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Pamela Mackey, Aneta Turlik, Kaori Ando, Mark E. Light, K. N. Houk, Gerard P. McGlacken
Summary: The study demonstrates the stereoselective formation of 5 contiguous chiral centers in a single pot reaction using aldol, aldol-Tishchenko reaction of N-tert-butyl sulfinimines. The researchers synthesized a series of cyclic and acyclic 3-amino-1,5-diol derivatives with high yields and excellent diastereoselectivities. The investigation supports two reversible aldol steps and a remarkably selective, irreversible Tishchenko reduction.
Article
Chemistry, Organic
Suman Sar, Prasanta Ghorai
Summary: In this study, a highly stereo-selective P(NMe2)3 mediated intramolecular deoxygenative umpolung cascade Michael addition-initiated cyclopropanation with a diverse substrate adaptability is disclosed. This methodology allows for the expedient access to valuable 6,5,3-fused scaffolds having an all-carbon quaternary stereocenter via Kukhtin-Ramirez (K-R) adduct formation, with excellent diastereoselectivity and yields under metal-free ambient conditions. Few functional group transformations have also been successfully performed, and an asymmetric catalytic attempt using (R)-(+)-H8-BINOL has delivered good enantioselectivity.
Article
Chemistry, Organic
Suman Sar, Prasanta Ghorai
Summary: In this study, we report a highly selective P(NMe2)3 mediated intramolecular deoxygenation reaction which exhibits excellent substrate adaptability. This methodology provides a convenient access to valuable 6,5,3-fused scaffolds with an all-carbon quaternary stereocenter via Kukhtin-Ramirez (K-R) adduct formation, achieving high diastereoselectivity and yields under metal-free ambient conditions. Furthermore, successful functional group transformations and enantioselective catalytic attempts have been achieved using (R)-(+)-H8-BINOL.
Article
Chemistry, Multidisciplinary
Michael G. J. Doyle, Alexis L. Gabbey, Wesley McNutt, Rylan J. Lundgren
Summary: In this study, electron-deficient arylacetates were utilized as benzyl nucleophile surrogates to successfully generate enantioenriched acyclic molecules containing quaternary carbon centers via a two-step substitution-decarboxylation process. Products were often obtained with >90% ee using a commercially available catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Bendu Pan, Jia-Sheng Ouyang, Yaqi Zhang, Hao Liang, Qiang Ni, Bin Chen, Xiaoyun Pu, Long Jiang, Rihui Cao, Liqin Qiu
Summary: The iridium-catalyzed intramolecular asymmetric allylic etherification of salicylic acid derivatives was successfully achieved for the first time, producing novel chiral 1,4-benzoxazepinones with good yields and high enantioselectivities. Compared to other ligands, L7 showed obvious advantages in catalytic activity and enantioselectivity. The method demonstrated mild conditions and a wide substrate scope, making it practical for application.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Manju Devi, Amol P. Jadhav, Ravi P. Singh
Summary: The stereoselective synthesis of 3,3'-disubstituted oxindoles with all-carbon quaternary stereocenters using KOH as a base has been achieved with an excellent diastereomeric ratio of 98:2. The practicality of the methodology has been demonstrated through the synthesis of a series of substrates with good to excellent yields. The aesthetic simplicity, accessibility, and eco-friendly nature of the base (KOH) have led to the broader application of this methodology in organic synthesis.
NEW JOURNAL OF CHEMISTRY
(2021)
