Article
Chemistry, Physical
Wei-Song Zhang, Ding-Wei Ji, Ying Li, Xiang-Xin Zhang, Chao-Yang Zhao, Yan-Cheng Hu, Qing-An Chen
Summary: A divergent regio- and stereoselective diarylation of dienes has been developed under Ni/Cr cocatalysis without the inherent driving force for the formation of polar metal alkoxides. Experimental studies have shown the key roles of Ni, Cr, and redox-active bis(imino)pyridine (PDI) ligands. The proposed mechanism suggests the involvement of organonickel species in the formation of the newly created C-C bond.
Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Vidmantas Bieliunas, Sigitas Stoncius
Summary: The design and synthesis of second generation C-2-symmetric ligands with additional substituents was reported. These substituents provide a further element for fine-tuning the ligand structure by enforcing conformational rigidity. The tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were successfully employed in the rhodium-catalyzed arylation reaction with good to excellent yields and enantioselectivities up to 99% ee.
Article
Chemistry, Multidisciplinary
Zhi-Zhou Pan, Jia-Heng Li, Hu Tian, Liang Yin
Summary: A copper(I)-catalyzed asymmetric allylation of ketones with 2-aza-1,4-dienes has been demonstrated, providing a series of functionalized homoallyl tertiary alcohols with high to excellent enantioselectivity. The deprotonation of N-allyl-1,1-diphenylmethanimines is the rate-determining step in the reaction, generating nucleophilic allyl copper(I) species. The utility of this method has been demonstrated by the asymmetric synthesis of (R)-boivinianin A and (R)-gossonorol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
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, Multidisciplinary
Barry M. Trost, Zhijun Zuo
Summary: A novel Pd-0-catalyzed highly selective [3+2] spiroannulation reaction has been developed for rapid assembly of a new class of [5,5] spirocyclic carbo- and heterocycles. The regioselectivity of the reaction can be controlled by fine-tuning the Pd-pi-allyl intermediate, with excellent toleration of various coupling partners and enantioselectivities demonstrated through further transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Lingpu Meng, Jingjie Yang, Mei Duan, You Wang, Shaolin Zhu
Summary: Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed using NiH catalysis with a simple bioxazoline ligand under mild conditions. A variety of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by employing nitroarenes, hydroxylamines and dioxazolones as amination reagents. Chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xian-Xiao Chen, Hao Luo, Ye-Wei Chen, Yang Liu, Zhi-Tao He
Summary: Chain walking has been an efficient method for the functionalization of inert C(sp(3))-H bonds, but it has limitations on mono-olefin migration and functionalization. In this study, we demonstrate the feasibility of tandem directed simultaneous migrations of remote olefins and stereoselective allylation. The use of palladium hydride catalysis and secondary amine morpholine as a solvent is crucial for achieving high substrate compatibility and stereochemical control.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Andrea Chaves-Pouso, Andres M. Alvarez-Constantino, Martin Fananas-Mastral
Summary: Allylic gem-dichlorides can be efficient substrates for catalytic asymmetric allylboration of alkynes. The method generates chiral skipped dienes with excellent levels of chemo-, regio- enantio- and diastereoselectivity, making them versatile building blocks for the synthesis of optically active compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shang Gao, Jiaming Liu, Diego Troya, Ming Chen
Summary: This article reports a copper-catalyzed reaction that can synthesize ketone compounds with high enantioselectivity and excellent enantioenrichment, providing a valuable platform for further chemical transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dipshi Singh, T. V. RajanBabu
Summary: We report two distinctly different, catalyst-dependent, modes of regio- and enantioselective cycloaddition reactions between alkynes and 1,3-dienes providing rapid access to highly functionalized 1,4-cyclohexadienes or cyclobutenes from the same precursors. Complexes of an earth abundant metal, cobalt, with several commercially available chiral bisphosphine ligands with narrow bite angles catalyze [4+2]-cycloadditions with excellent chemo-, regio- and enantioselectivities. In contrast, complex of a finely tuned phosphino-oxazoline ligand promotes unique [2+2]-cycloaddition between the alkyne and the terminal double bond of the diene giving a highly functionalized cyclobutene with excellent regio- and enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Bo-Ying Yao, Wei-Guo Xiao, Li-Jun Xiao, Qi-Lin Zhou
Summary: A method for hydroalkynylation reaction of 1,3-dienes with simple alkynes using an efficient nickel catalyst system and Xantphos ligand is presented. This method overcomes previous constraints in 1,3-diene hydroalkynylation and offers a convenient and direct means for obtaining a wide range of allylic alkynes.
Article
Chemistry, Physical
Dan Forster, Weisi Guo, Qian Wang, Jieping Zhu
Summary: Dual photoredox-transition-metal catalysis is a powerful tool in chemical transformations, but its use in the selective difunctionalization of 1,3-dienes has been underexplored. Here, we report an enantioselective 1,2-amidocyanation of 1,3-dienes using synergistic action of photoredox and copper catalysts. The reaction proceeds under visible-light irradiation and produces three-component adducts with good to high yields and high regio- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Changli He, Xiaoxue Tang, Xin He, Yuqiao Zhou, Xiaohua Liu, Xiaoming Feng
Summary: Reversal of regioselectivity in the catalytic asymmetric conjugate additions of 3-substituted oxindoles to beta-nitroenones or beta-nitroacrylates was achieved with chiral scandium catalysts. Functionalized 3,3-disubstituted oxindoles, including terminal and internal vinyl groups, were constructed in excellent yields and ee values.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Tian-Yuan Zhao, Li-Jun Xiao, Qi-Lin Zhou
Summary: A nickel-catalyzed desymmetric reductive cyclization/coupling of 1,6-dienes has been developed, providing an efficient method for constructing a chiral tertiary alcohol and a quaternary stereocenter by a single operation. The method exhibits excellent diastereoselectivity and high enantioselectivity, has a broad substrate scope, and shows good tolerance of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
