Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
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
Changpeng Chen, Wenqing Guo, Deyong Qiao, Shaolin Zhu
Summary: We report a NiH-catalyzed asymmetric migratory hydroalkylation process for the efficient and selective construction of enantioenriched multi-substituted cycloalkanes. Through a dynamic kinetic asymmetric transformation (DYKAT), easily accessible racemic and isomeric mixtures of cycloalkenes could be directly utilized as starting materials, convergently producing highly regio-, diastereo-, and enantioselective chiral 1,2-cis disubstituted cycloalkanes. In addition, prochiral cyclic alkenes can also be employed, delivering chiral 1,2-cis disubstituted cycloalkanes through desymmetrization process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiandong Liu, Hegui Gong, Shaolin Zhu
Summary: A NiH-catalyzed migratory hydroalkenylation reaction of olefins with alkenyl bromides has been developed, yielding benzylic alkenylation products with high yields and excellent chemoselectivity. The mild conditions of the reaction prevent olefinic products from further isomerization or subsequent alkenylation, and catalytic enantioselective hydroalkenylation of styrenes was achieved using a chiral bisoxazoline ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Leipeng Xie, Jimin Liang, Haohao Bai, Xuanyu Liu, Xiao Meng, Yuan-Qing Xu, Zhong-Yan Cao, Chao Wang
Summary: In this paper, a ligand-controlled, directing-group-assisted strategy was reported to promote NiH-catalyzed site-selective hydroamination of unactivated alkenes. Proper bidentate nitrogen-containing ligands were used to achieve good-to-excellent regioselectivity for the synthesis of 1,1-, 1,2-, and 1,3-diamines from the same substrates. Various O-benzoylhydroxylamine electrophiles with different functional groups can be installed via Ni migration or nonmigration. These protocols provide a method for the enantioselective synthesis of valuable 1,2-diamines and 1,3-diamines.
Article
Chemistry, Multidisciplinary
Jian Chen, Lifu Wu, Yue Zhao, Shaolin Zhu
Summary: In this study, we report a catalytic reaction that can control two stereocenters simultaneously. By using a chiral catalyst, we achieved simultaneous control of the stereocenters in two substrates, resulting in the formation of high-value products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhan Dong, Qiongyao Tang, Changyu Xu, Li Chen, Haiting Ji, Sitian Zhou, Liangliang Song, Liang-An Chen
Summary: Transition-metal catalyzed intermolecular 1,2-diarylation of electronically unactivated alkenes is a widely studied topic, but most examples are limited to terminal alkenes. Furthermore, the asymmetric 1,2-diarylation of unactivated alkenes remains unsolved and is challenging. In this study, a highly efficient directed nickel-catalyzed reductive 1,2-diarylation of unactivated internal alkenes with high diastereoselectivities is described. Moreover, enantioselective 1,2-diarylation of unactivated terminal and challenging internal alkenes is achieved with good to high enantioselectivities and high diastereoselectivities by generating a cationic Ni-catalyst through the addition of alkali metal fluoride.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Fang Zhou, Shaolin Zhu
Summary: Here, a chiral selective nickel-hydride catalyzed hydroalkylation method is reported for the synthesis of structurally diverse beta-chiral amides from readily accessible beta-alkyl-alpha,beta-unsaturated amides. The regio-reversed hydronickellation process provides a complementary approach to access enantioenriched beta-functionalization amides with a stereocenter at the beta-position.
Article
Chemistry, Physical
Jitao Xu, Zhilong Li, Yumin Xu, Xiaomin Shu, Haohua Huo
Summary: This study presents an enantioselective benzylic C(sp(3))-H alkenylation of alkylarenes with vinyl bromides via photoinduced nickel catalysis, allowing for the stereodivergent synthesis of enantioenriched Z- and E-alkenes bearing aryl-substituted, allylic tertiary stereogenic centers. The tunable Z/E-selectivity is achieved by energy transfer catalysis with choice of the photocatalyst counteranion, showcasing simple starting materials, mild reaction conditions, broad substrate scope, divergent Z- and E-selectivities, and high enantioselectivities. Additionally, a formal asymmetric benzylic C(sp(3))-H alkylation can be achieved through a one-pot alkenylation/reduction sequence, providing a complementary strategy for stereochemical control in C(sp(3))-C(sp(3)) bond construction.
Article
Chemistry, Organic
Yun-Xuan Tan, Xing-Yu Liu, Cheng-Yu He, Ping Tian
Summary: This study presents a Rh(III)-catalyzed asymmetric carboboration of heterobicyclic alkenes, including 7-oxa- and 7-azabenzonorbornadienes, achieving the transformation with high yields and excellent enantioselectivities. The product bearing seven chiral centers was efficiently obtained, and several transformations of the carboboration product were also demonstrated.
Article
Chemistry, Multidisciplinary
Marc Devillard, Nour Nour Eddine, Marie Cordier, Gilles Alcaraz
Summary: A straightforward synthetic methodology for the preparation of photochromic siloles based on the dithienylethene motif has been developed. This method relies on an efficient palladium-catalyzed annulation reaction of a 2,3-bis(3-thienyl)-silirene with terminal alkynes in mild conditions. The reaction is functional group-tolerant and can be extended to the synthesis of photochromic polymers with different degrees of photochromic unit incorporation by adjusting the polymer/silirene stoichiometric ratio.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yuanyuan Zhang, Yaoyu Liang, Xiaodan Zhao
Summary: The enantioselective electrophilic three-component thioarylation of alkenes using chiral selenide catalysis with free phenols as arylating sources has been disclosed. Various chiral phenols were obtained in high regio-, enantio-, and diastereoselectivities. Mechanistic studies showed that the transformation proceeded through carbon nucleophilic attack to give the products rather than the intramolecular rearrangement of phenolic ether intermediates.
Review
Chemistry, Multidisciplinary
Jonathan Bock, Sudip Guria, Volker Wedek, Ulrich Hennecke
Summary: The dihalogenation of alkenes is a classic reaction in organic chemistry and typically exhibits anti-selectivity. Recent progress in reagent-controlled, enantioselective dihalogenation has been made, but challenges still remain in this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Tanuja Tewari, Rohit Kumar, Samir H. Chikkali
Summary: An iron-catalyzed, magnesium-mediated, formal hydroformylation method for alkynes and alkenes in the absence of syngas has been reported. The reaction proceeds with good to excellent conversion and selectively produces alpha,beta-unsaturated aldehydes. Mechanistic investigations revealed the presence of vinyl magnesium intermediate, and the control experiment confirmed the iron catalyst's homogeneous nature.
Article
Chemistry, Multidisciplinary
Daqi Lv, Qiao Sun, Huan Zhou, Liang Ge, Yanjie Qu, Taian Li, Xiaoxu Ma, Yajun Li, Hongli Bao
Summary: This study reports the iron-catalyzed intermolecular asymmetric aminoazidation and diazidation of styrenes, providing a direct and efficient pathway for constructing chiral nitrogen-containing compounds. The method shows potential value in the synthesis of chiral organoazides, with relatively low loading of catalyst and chiral ligand required for practical application.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
