Article
Chemistry, Organic
Wangyu Li, Dungai Wang, Xiao Liang, Zhixiong Jin, Shiwen Zhou, Guanru Chen, Yuanjiang Pan
Summary: A Lewis acid-catalyzed selective reaction for the synthesis of diarylmethanes or oxoimidazolidines from anilines and glyoxylates was developed. The reaction yielded a series of aniline-based diarylmethanes and stereoselective oxoimidazolidines, depending on the catalyst used.
Article
Chemistry, Multidisciplinary
Anton Kudashev, Olivier Baudoin
Summary: A ligand-controlled site-selective C(sp(3))-H arylation of heteroaromatic ketones has been developed using Pd catalysis, with selective reactions occurring at the alpha- or beta-position of the ketone side-chain. Addition of a pyridone ligand enables switching from alpha- to beta-arylation. The alpha-arylation process demonstrates broad scope and high site- and chemoselectivity, while the beta-arylation is more limited, with mechanistic investigations suggesting different pathways for the two processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Garrett P. R. Freure, Eric A. Skrotzki, Jean-Danick E. Lavertu, Stephen G. Newman
Summary: Various methods have been investigated recently for the arylation of weakly acidic C(sp(3))-H bonds, with this study focusing on a base-mediated approach using organometallic superbases. The study developed conditions for high selectivity metalation using either n-BuLi/diamine or n-BuLi/KOtBu superbases, allowing for direct use in cross-coupling or formation of organozincs for reactions with functional groupdense organohalides.
Article
Chemistry, Physical
Zengbing Bai, Qingqing Chen, Jun Gu, Chuangxu Cai, Jie Zheng, Wangjian Sheng, Shandong Yi, Fang Liu, Huan Wang
Summary: The paper introduces a versatile strategy based on late-stage palladium-catalyzed C-H activation for synthesizing peptides with backbone thiazole motifs, enabling site-selective arylation in peptide side chains and expanding the structural diversity of peptide compounds. This method exhibits high biocompatibility and is capable of efficiently constructing peptide libraries with featured backbone thiazole units.
Article
Chemistry, Physical
Yi-Hao Li, Yuxin Ouyang, Nikita Chekshin, Jin-Quan Yu
Summary: Pd(II)-catalyzed gamma-C(sp3)-H (hetero)arylation of aliphatic ketones using alpha-amino acids as transient directing groups (TDG) has been developed. By reducing the loading of acid additives, the crucial ligand effect of 2-pyridone is enhanced, leading to improved reactivity and the possibility of cyclic gamma-methylene C(sp3)-H arylation of ketones. Mechanistic investigation and comparison to the gamma-C-H arylation of aldehydes provide structural insights for designing site-selective TDGs.
Article
Chemistry, Multidisciplinary
Jianxia Chen, Chaolumen Bai, Hongpeng Ma, Dan Liu, Yong-Sheng Bao
Summary: This study reports the first example of heterogeneous palladium catalyzed C(sp(3))-H bonds arylation by a transient-ligand-directed strategy. Supported palladium nanoparticles were used as catalyst to assemble a library of highly selective and functionalized o-benzylbenzaldehydes. The catalyst showed good stability and activity over multiple runs.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Ziyi Yang, Yuanbo Wu, Yatong Fu, Jianxin Yang, Jian Lu, Ju-You Lu
Summary: A palladium-catalyzed selective B(3)-H arylation of o-carboranes at room temperature has been developed, using readily available arylboronic acids as the aryl source. The method provides an efficient synthetic route for constructing polysubstituted o-carborane derivatives.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
De Wang, Zefeng Song, Jianyu Zhang, Tao Xu
Summary: A novel remote delta methylene C(sp(3))-H functionalization was discovered, catalyzed by an organophosphine through alkyne isomerization/conjugate addition cascade without the need for a classical electron-withdrawing group. The process, under only 10 mol% of PMe2Ph with a catalytic proton shuttle, successfully produced a large group of functionalized products with good diastereoselectivity. Mechanistic studies and fluorescence properties of the conjugated polyene products were investigated in detail.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Rhys A. Lippa, David J. Battersby, John A. Murphy, Tim N. Barrett
Summary: The synthesis of substituted arylethylamines via palladium-catalyzed coupling between (chloromethyl)aryls and N,N-dialkylaminomethyltrifluoroborate salts was reported in this study. Rapid hit identification was achieved using microscale high-throughput experimentation, followed by millimolar-scale reaction parameter optimization. A range of structurally and electronically varied arylethylamine products were obtained in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Zhuo Wu, Zechen Wu, Xueliang Sun, Weixin Qi, Zhengyang Zhang, Yanghui Zhang
Summary: The study presents a Pd-catalyzed intramolecular coupling of inert C(sp(3))-H and C(sp(2))-H bonds, leading to the formation of organic compounds.
Article
Chemistry, Organic
Liming Yang, Henan Xie, Guanghui An, Guangming Li
Summary: In this study, a new method was developed to enhance the coordination of Pd catalysts with weak-coordinating substrates using a commercially available sulfonic acid, enabling arylation and alkenylation of C(sp(3))-H bonds of Weinreb amides.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Qiu-Cui Zheng, Si-Yuan Peng, Si-Qi Cong, Xin-Yu Ning, Yan Guo, Meng-Jiao Li, Wen-Shu Wang, Xiao-Jie Cui, Fei-Xian Luo
Summary: In this study, an unexpected dehydrogenation reaction was successfully explored through C(sp3)-H arylation and C-N coupling, leading to the synthesis of bioactive compounds with good regioselectivity and functional group compatibility. This research provides an alternative pathway to achieve molecular complexity and diversity through multiple C-H bond activations.
Article
Chemistry, Organic
Dejiang Zhang, Zhi Xu, Ting Tang, Liyuan Le, Cairong Wang, Nobuaki Kambe, Renhua Qiu
Summary: In this study, a general method for the synthesis of unsymmetric diarylmethanes from (hetero)aryl methylhalides and Sb-aryl stibines is described. The protocol has a broad substrate scope and good functional group tolerance. Gram-scale synthesis of drug molecules and their derivatives was efficiently achieved using this method.
Article
Chemistry, Multidisciplinary
Xuchao Wang, Jing Xue, Zi-Qiang Rong
Summary: This study reports a highly efficient catalyst-tuned regio- and enantioselective hydroalkylation reaction for the divergent synthesis of chiral C2- and C3-alkylated pyrrolidines. The reaction uses readily available catalysts and chiral ligands to synthesize enantioenriched compounds with excellent regio- and enantioselectivity. It also demonstrates compatibility with complex substrates derived from a series of drugs and bioactive molecules, providing a distinct entry to more functionalized chiral N-heterocycles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Md. Emdadul Hoque, Jin-Quan Yu
Summary: In this study, we report a new method for the gamma-arylation and gamma-lactonization of aliphatic acids, enabled by a L,X-type CarboxPyridone ligand catalyzed Pd(II) reaction. A wide range of gamma-arylated gamma-lactones can be efficiently synthesized in a single step, and the arylated lactones can be further converted into disubstituted tetrahydrofurans, which are prominent scaffolds in bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)