Article
Chemistry, Multidisciplinary
Hao-Dong Qian, Zhi-Heng Li, Shuang Deng, Chaochao Yao, Hua-Ming Xiang, Guang Xu, Zi-Qi Geng, Zihao Wang, Linfeng Chen, Chunrong Liu, Cuiju Zhu, Xiaotian Qi, Hao Xu
Summary: Distinct regio- and enantioselectivity control has been achieved in copper-catalyzed vinylogous and bisvinylogous propargylic substitution using a novel chiral N,N,P ligand. The developed method provides an efficient and selective approach to the synthesis of enantioenriched alkynyl unsaturated carbonyl compounds, with excellent functional group tolerance and broad substrate scope. The synthetic utility of the developed method is demonstrated by gram-scale synthesis and application to the enantioselective synthesis of challenging compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Thomas Hansen, Pascal Vermeeren, Lea de Jong, F. Matthias Bickelhaupt, Trevor A. Hamlin
Summary: The study explores the competition between S(N)2 and S(N)2' pathways in bimolecular nucleophilic substitution reactions at allylic systems, providing a model to explain under which circumstances a nucleophile will follow either pathway. Activation strain analyses reveal the physical factors behind the S(N)2/S(N)2' competition, demonstrating that concepts like reaction characteristics and transition state acidity can help predict reactivity trends in organic synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Panchi Guo, Miao Zhan
Summary: A newly developed iridium-catalyzed enantioconvergent coupling reaction allows for the synthesis of various chiral homoallylic organoboronic esters with good yields and excellent enantioselectivities. The synthetic practicality of the products was demonstrated by their conversion to other useful families of compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Yeosan Lee, Seungcheol Han, Seung Hwan Cho
Summary: Chemical and stereoselective transformations of polyborylalkanes are powerful methods to access optically active molecules efficiently. Gem-diborylalkanes, as versatile synthetic handles, can generate key intermediates for various enantioselective reactions. Catalytic reactions using gem-diborylalkanes can rapidly access diverse enantioenriched organoboron compounds for further transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Qi Zhang, Si-Wei Zhou, Chang-Yun Shi, Liang Yin
Summary: A catalytic asymmetric allylic substitution using copper(I) homoenolates as nucleophiles has been achieved, with high yields and enantioselectivity. The method is applicable to a broad range of substrates and can be extended to the construction of chiral quaternary carbon centers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yang Liu, Linghong Zhang, Yong Zhang, Shanshan Cao, Xu Ban, Yanli Yin, Xiaowei Zhao, Zhiyong Jiang
Summary: In this article, a photoredox catalytic hydrogen atom transfer (HAT) and enantioselective protonation strategy for asymmetric olefin isomerization is reported. A dual catalyst system involving a visible light photosensitizer DPZ and a chiral phosphoric acid is established, with the assistance of N-hydroxyimide to perform HAT. This strategy enables the synthesis of a wide array of allylic azaarene derivatives with high yields, ees, and E/Z ratios, highlighting its broad applicability and promising utility.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: This study reveals a novel iron-catalyzed para-C-H allylation reaction of aniline derivatives via a chelation-induced strategy, providing various allylic arenes with good yields and selectivity.
Article
Chemistry, Organic
Qiulin You, Xin Xiao, Yang Shi, Yimin Wu, Guangying Tan
Summary: Transition-metal-catalyzed directed C-H allylation of arenes is an efficient method to construct value-added allylic arenes. This study presents a novel iron catalyst and a chelation-induced strategy for the para-C-H allylation of aniline derivatives, which provides good yields and excellent selectivity.
Article
Chemistry, Physical
Andrea Chaves-Pouso, Eva Rivera-Chao, Martin Fananas-Mastral
Summary: This Perspective covers the developments in the area of catalytic allylboration of alkynes and highlights the key features that have allowed for the control of the regio-, diastereo-, and enantioselectivity in these transformations.
Article
Chemistry, Organic
Xiangbin Bai, Linlin Qian, Hong-Hao Zhang, Shouyun Yu
Summary: This study presents an enantioselective radical alkylation of 4-alkyl-1,4-dihydropyridines with Morita-Baylis-Hillman (MBH) adducts using dual photoredox/palladium catalysis, yielding products with good yields and enantioselectivity. The use of Ding's spiroketal-based bis-(phosphine) (SKP) ligand is crucial for achieving satisfactory regio- and enantioselectivity in this reaction. The resulting alpha,beta-unsaturated ester can be easily reduced to a synthetically useful chiral allyl alcohol.
Article
Chemistry, Multidisciplinary
Minjae Kim, Bohyun Park, Minkyeong Shin, Suyeon Kim, Junghoon Kim, Mu-Hyun Baik, Seung Hwan Cho
Summary: A copper-catalyzed enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides was reported in this study. The combination of copper(I) bromide and H-8-BINOL derived phosphoramidite ligand proved to be the most effective catalytic system, providing various enantioenriched homoallylic boronate esters under mild conditions. Experimental and theoretical studies elucidated the reaction mechanism and revealed the enatiotopic-group-selective trans-metalation of gem-diborylalkanes with chiral copper complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Wei Liu, Le Zhang, Ye Liu, Shi-Lu Fan, Jian-Jun Dai, Wei Tao, Hui-Xia Zhu, Hua Xiao
Summary: In this study, a consecutive S(N)2'/S(N)2'' addition of phenol to gamma-vinyl MBH carbonate was performed, leading to the formation of functionalized exocyclohexenes with excellent chemoselectivity. Additionally, using o-hydroxychalcones as pronucleophiles, a series of pharmaceutically intriguing tricyclic chromane derivatives were selectively synthesized through an S(N)2'/S(N)2''/intramolecular Diels-Alder reaction sequence with good diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Eleanor Bowen, Gillian Laidlaw, Bethany C. Atkinson, Timur A. McArdle-Ismaguilov, Vilius Franckevicius
Summary: In this study, a palladium-catalyzed decarboxylative asymmetric allylic alkylation reaction was developed to access enantioenriched heterocyclic sulfones. The reaction showed high levels of enantioselectivity and provided a new pathway for the synthesis of stereodefined cyclic sulfones for medicinal chemistry applications.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Irene Sanchez-Sordo, Andrea Chaves-Pouso, Jaime Mateos-Gil, Eva Rivera-Chao, Martin Fananas-Mastral
Summary: In this study, a new copper-catalyzed coupling reaction is reported for the enantioselective desymmetrization of chiral cycloalkenes. The method allows for the synthesis of chiral products with high regio-, diastereo-, and enantioselectivity, which can serve as versatile building blocks for the synthesis of various optically active cyclic compounds.
Article
Chemistry, Organic
Kento Asai, Masahiro Miura, Koji Hirano
Summary: A palladium-catalyzed cross-coupling reaction between diarylmethanol derivatives and diborylmethane has been developed, delivering the corresponding homobenzylic boronates in good yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
