Article
Chemistry, Organic
Lin Zhu, Jie Huang, Fanling Meng, Ziyun Tan, Xiao Meng, Yang Xiao, Lanlan Zhang, Wenyi Li, Chao Wang
Summary: A NiH-catalyzed migratory and non-migratory gem-difluoroallylation reaction of alkenyl amines with trifluoromethyl alkenes has been developed. This reaction offers high selectivity and diversity for the synthesis of fluoro-containing amines, which is beneficial for drug discovery.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Rong-De He, Yunfei Bai, Guan-Yu Han, Zhen-Zhen Zhao, Xiaobo Pang, Xiaobo Pan, Xue-Yuan Liu, Xing-Zhong Shu
Summary: This study successfully reported a cross-electrophile reaction of alkenyl acetates with alkyl bromides, establishing a new method for the synthesis of aliphatic alkenes that can add more structural complexity and molecular diversity with enhanced functionality tolerance. Preliminary mechanistic studies suggest that the Ni-I species plays a crucial role in the coupling of these two reactivity-mismatched electrophiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xiaowei Li, Yuxiu Li, Wenlong Shan, Zemin Wang, Ruihua Liu, Zhong Zhang, Xiangqian Li, Dayong Shi
Summary: Here we report the development of a Ni-catalyzed defluorinative cross-electrophile coupling of gem-difluoroalkenes with alkenyl electrophiles, enabling the formation of C(sp(2))-C(sp(2)) bonds. The reaction exhibits broad functional group compatibility and excellent stereoselectivity, providing access to various monofluoro 1,3-dienes. Additionally, we demonstrate the synthetic transformations and applications of this reaction for the modification of complex compounds.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Renshi Luo, Yuqiu Liang, Sen Wang, Jianhua Liao, Lu Ouyang
Summary: Here, we disclose a new iridium-catalyzed and acid-promoted process for selective para-alkylation of anilines and phenols using aryloxy or alkoxy aryl alkynes as the alkylated sources. This method delivers a wide range of para-C-alkylated phenols and anilines in good to excellent yields. The promising application in organic synthesis is evidenced by the low catalyst loading, scale-up of synthesis, operation under air conditions, and recycling of catalyst (5 times without deactivation).
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Shuhui Lu, Zhifei Zhao, Yingzheng Ren, Guangfen Du, Jixing Zhao, Shi-Wu Li
Summary: The first highly enantioselective asymmetric vinylogous Michael addition of alpha,alpha-dicyanoalkenes with 3-alkenyl-oxindoles catalyzed by chiral-at-metal complexes has been successfully developed. The reaction delivers 3,3’-disubstituted oxindoles with an all-carbon quaternary stereocenter. This approach exhibited excellent advantages in terms of enantioselectivity, catalyst loading, and yield.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yinan Ai, Hanlin Yang, Chunying Duan, Xingwei Li, Songjie Yu
Summary: A new Co-catalyzed sequential C-C and C-F activation of gem-difluorinated cyclopropanes has been developed, allowing the formation of nucleophilic fluoroallylcobalt, followed by addition to aldehydes to yield linear (Z)- and (E)-fluorinated homoallylic alcohols. This discovery established a new strategy for the efficient transformation of gem-difluorinated cyclopropanes and synthesis of challenging fluorinated homoallylic alcohols.
Article
Chemistry, Organic
Qu-Ping Hu, Jing Cheng, Ying Wang, Jie Shi, Bi-Qin Wang, Ping Hu, Ke-Qing Zhao, Fei Pan
Summary: The study presents a photocatalyzed transformation for the remote site-selective functionalization of unactivated C(sp(3))-H bonds in amides, resulting in gem-difluoroalkenes with trifluoromethyl-substituted alkenes. The site selectivity is controlled by a 1,5-hydrogen atom transfer (HAT) process of the amide, showing both chemo- and site-selectivity for the formation of secondary, tertiary, or quaternary carbon centers.
Article
Chemistry, Physical
Leiyang Lv, Huijun Qian, Anna B. Crowell, Shuming Chen, Zhiping Li
Summary: This study reports a catalytic method for controlling the selectivity of reactions, allowing access to diverse fluorinated 1,5-dienes from the same starting materials. Density functional theory calculations also revealed a ligand design for switching selectivity. This ligand-controlled approach is important for late-stage modification of complex molecules.
Article
Chemistry, Multidisciplinary
Leiyang Lv, Chao-Jun Li
Summary: A cooperative strategy has been developed to switch the reaction selectivity from beta-fluoroalkene scaffolds to alkylated alpha-fluoroalkene skeletons. Key factors include the unique reactivity of hydrazones and the assistance of a steric-embedded N-heterocyclic carbene ligand. This approach allows for efficient functionalization of various gem-difluorocyclopropanes under mild conditions, including modified pharmaceutical and biological molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Shiji Xu, Qiang Wang, Jing Sun, Ying Han, Weiming Hu, Lei Wang, Chao-Guo Yan
Summary: In this study, Pd/Cu-catalyzed cascade Heck-type reactions between alkenyl halides and terminal alkynes have been developed. This research provides an efficient atom-economical approach to access a variety of highly substituted pyrrolidines in moderate to good yields. This protocol features readily available substrates, broad substrate scope, easy scale-up, high selectivities, and versatile transformations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Jingchao Jiao, Yapeng Yan, Qiumin Ke, Yusen Zhang, Hang Huang, Qianwen Gao, Jie Liu, Xi Wang
Summary: Here, an efficient and green paired electrolysis strategy for decarboxylative coupling of alkenyl acids with diazo compounds is reported, providing a wide range of beta,gamma-alkenyl esters and amides. The method exhibits high stereoselectivity and avoids the use of transition metals and chemical redox regents. Additionally, the protocol allows for the easy synthesis of dideuterated products with a high deuterium incorporation level (93-99% D-inc.) by directly utilizing D2O, highlighting its significant value.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Woohyun Jo, Jun Hee Lee, Seung Hwan Cho
Summary: This feature article summarises recent progress in the synthetic utilisation of alpha-borylcarbanions, including carbon-carbon bond formation with alkyl halides, alkenes, N-heteroarenes, and carbonyls. Carbon-boron bond formation in organohalides mediated by alpha-borylcarbanions is also summarised.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Yan Mao, Wenxi Chen, Changchang Li, Lin Miao, Yanfei Lin, Fei Ling, Zhangpei Chen, Jinzhong Yao
Summary: An efficient method for constructing various 3,4,5-trisubstituted phenol derivatives has been developed using Rh(iii)-catalyzed coupling of phosphonium cations with internal alkynes. The protocol exhibits good substrate compatibility, with structurally and electronically diverse phosphonium compounds reacting efficiently with yields up to 87%.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Roshan K. Dhungana, Albert Granados, Mohammed Sharique, Jadab Majhi, Gary A. Molander
Summary: Here, a three-component organophotoredox coupling of N-alkenyl amides with alpha-bromocarbonyls and various nucleophiles is reported. This transition metal-free difunctionalization protocol sequentially installs C-C and C-Y (Y = S/O/N) bonds in alkenes. This reaction works with different types of alkenes containing amides.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Si-Kai Liu, Pei-Hsuan Chien, Bo-Wei Huang, Jeng-Liang Han
Summary: In this study, a site-selectivity switchable Friedel-Crafts reaction of 1-naphthols and 2,3-dioxopyrrolidines was developed using organocatalyst control. Chiral tertiary amines were used for o-selective reaction, while Bronsted acids or Lewis acids were used for p-selective reaction. The protocol enabled the preparation of a range of functionalized polycyclic 2-pyrrolidinone derivatives. Theoretical mechanistic investigations provided insights into the reaction pathway and chiral induction for the o-selective Friedel-Crafts reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
