Article
Chemistry, Multidisciplinary
Benedikt S. Schreib, Mina Son, Francoise A. Aouane, Mu-Hyun Baik, Erick M. Carreira
Summary: In this study, a Pd-catalyzed C-H alkenylation reaction of electronically unbiased allenes was reported, providing penta-1,2,4-triene products in up to 94% yield. The use of picolinamide directing group enabled the formation of allenyl-palladacycles, which subsequently participated in a turnover-limiting Heck-type reaction with electron-deficient alkene coupling partners. Additionally, picolinamide N,O-acetals were introduced as readily removable auxiliaries for C-H activation reactions, facilitating the efficient alkenylation of allenyl carbinol derivatives while maintaining the reactivity of the products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Hongxin Liu, Junqin Peng, Bin Li, Baiquan Wang
Summary: An efficient direct nucleophilic addition reaction of C(sp2)-H bonds to aldehydes catalyzed by a dimeric manganese has been developed. This reaction has a broad range of substrates, and high yields were also obtained with inert aliphatic aldehydes as substrates. A dimeric Mn2(CO)8Br2 was proven to be a more efficient catalyst precursor than the monomeric Mn(CO)5Br.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yongzheng Ding, Renbin Huang, Wei Zhang, Hanmin Huang
Summary: A catalytic system combining NiBr2 and diphenylphosphine oxide was developed for the direct synthesis of valuable arylacetic acids from inexpensive alkylarenes and H2O via oxidative carbonylation. This method is compatible with alkylarenes containing primary and secondary benzylic C-H bonds, and the commonly used drugs ibuprofen and diclofenac can be easily obtained.
Article
Chemistry, Organic
Bhushanarao Dogga, C. S. Ananda Kumar, Jayan T. Joseph
Summary: An efficient protocol has been developed for the reductive carbonylation of (hetero) aryl halides and triflates under CO gas-free conditions using Pd/Co-2(CO)(8) and triethylsilane. The mild reaction conditions, enhanced chemoselectivity, and easy access to heterocyclic and vinyl carboxaldehydes highlight its importance in organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Raghunath Bag, Nagendra K. Sharma
Summary: This study presents a convenient synthetic method for the Pd-catalyzed picolinamide-directed site-selective C(sp(2))-H chalcogenation of alpha-amino acids and peptides. It has been successfully applied to the synthesis of a variety of alpha-amino acids, benzylamines, and phenethyl amines with moderate to good yields and good selectivity. Moreover, it allows for late-stage peptide chalcogenation and offers wide substrate scopes and various postsynthetic utilities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Lukass Lukasevics, Aleksandrs Cizikovs, Liene Grigorjeva
Summary: An efficient protocol for the C(sp(2))-H carbonylation of amino acid derivatives based on an inexpensive cobalt(II) salt catalyst is reported. The method utilizes picolinamide as a traceless directing group and Co(dpm)(2) as the catalyst, allowing for a broad range of phenylalanine derivatives bearing diverse functional groups to be tolerated. Moreover, the method can be successfully applied for the C(sp(2))-H carbonylation of short peptides, enabling access for peptide late-stage carbonylation.
Article
Multidisciplinary Sciences
Shao-Bai Yan, Rui Wang, Zha-Gen Li, An-Na Li, Chuanyong Wang, Wei-Liang Duan
Summary: This paper reports a Cu-catalyzed asymmetric C(sp(2))-H arylation using diaryliodonium salts, which enables the synthesis of a range of chiral phosphonic diamides and chiral phosphine oxide indoles with high selectivity under mild conditions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Wei-Hao Rao, Qi Li, Li-Li Jiang, Xue-Wan Deng, Pan Xu, Fang-Yuan Chen, Ming Li, Guo-Dong Zou
Summary: The copper-catalyzed intermolecular electrophilic amination of benzamides with O-benzoyl hydroxylamines was successfully achieved with the assistance of an 8-aminoquinolyl group, showing good compatibility with various aryl amides and heteroaryl amides as well as excellent tolerance to different functional groups. The monoaminated product was predominantly obtained under simple reaction conditions, and preliminary mechanistic investigations suggested C-H activation to potentially be the rate-determining step.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Lin Ma, Xiaohui Zhang, Yanyan Tuo, Qing-Zhong Zheng
Summary: An efficient Cp*Rh(III)-catalyzed regioselective C(sp(2))-H mono- and dialkynylation of thioamides was described. This reaction was performed under mild conditions with high yields, demonstrating versatility by controlled mono- and dialkynylation. The application of this approach in late-stage functionalization of two drug molecules (Adapalene and Amoxapine) was also demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Tang, Fengjie Lu, Yi Sun, Guodong Zhang, Ensheng Zhang, Yuan-Ye Jiang
Summary: The research presents an efficient and versatile strategy for site-selective fluorination and amination of phenylalanine-containing peptides via late-stage Pd-catalyzed d-C(sp(2))-H activation. This provides a valuable tool for the in situ synthesis of fluorinated indoline scaffolds within peptides.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Review
Chemistry, Organic
Jinhwan Park, Jongwoo Son
Summary: Metal-catalyzed C-sp2-H oxygenation is an important synthetic transformation that allows the incorporation of useful functional groups using a simple protocol. Cobalt catalysis, as a sustainable alternative, has gained attention due to its natural abundance and cost-effectiveness. In this Review, recent advances in cobalt-catalyzed C-sp2-H alkoxylation and acetoxylation are highlighted, along with discussions on various directing groups.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Youhao Wei, Zheng Wang, Kaifeng Wang, Jiang-Kai Qiu, Zhaoshan Wang, Haotian Li, Xiu Duan, Kai Guo, Xiaoguang Bao, Xinxin Wu
Summary: This study reports a copper-catalyzed allenic C(sp(2))-H cyanation with exceptional site-selectivity, addressing the challenge in synthetic chemistry of functionalizing allenic C(sp(2))-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Subhashree. S. S. Panda, Nagendra. K. K. Sharma
Summary: This report describes a new synthetic methodology for the ortho-arylation of arylamines and alpha-aromatic amino acids using a Pd-catalyzed C(sp(2))-H activation. The use of diethoxyethyl-l-proline as a transient directing group allows for the formation of mono-arylated arylamines as the major products using aryliodides. This method shows promise for the synthesis of various biphenyl amines and novel peptidomimetics.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Hirotsugu Suzuki, Fumito Sasamori, Takanori Matsuda
Summary: In this study, we developed a rhodium-catalyzed alkoxylcarbonylation/acylation method using anhydrides as the carbonyl source to synthesize C7-carbonylated indolines. This catalytic process is additive- and CO-free, and it successfully achieves the C-H acylation of indolines, leading to the formation of alpha-branched ketones that were difficult to prepare using previously reported analogous catalytic reactions.
Article
Chemistry, Physical
Zhoulong Fan, Shiqi Shu, Jiabin Ni, Qizheng Yao, Ao Zhang
Article
Chemistry, Organic
Jie Li, Yu Xue, Zhoulong Fan, Chunyong Ding, Ao Zhang
JOURNAL OF ORGANIC CHEMISTRY
(2017)
Article
Chemistry, Organic
Zhoulong Fan, Heng Lu, Wei Li, Kaijun Geng, Ao Zhang
ORGANIC & BIOMOLECULAR CHEMISTRY
(2017)
Article
Chemistry, Organic
Zhoulong Fan, Jie Li, Heng Lu, Dong-Yu Wang, Chao Wang, Masanobu Uchiyama, Ao Zhang
Article
Chemistry, Multidisciplinary
Zhoulong Fan, Heng Lu, Zhen Cheng, Ao Zhang
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Organic
Zhoulong Fan, Heng Lu, Ao Zhang
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Fan Wang, Hong Yang, Shujuan Yu, Yu Xue, Zhoulong Fan, Gaolin Liang, Meiyu Geng, Ao Zhang, Chunyong Ding
ORGANIC & BIOMOLECULAR CHEMISTRY
(2018)
Article
Chemistry, Organic
Heng Lu, Zhoulong Fan, Chaodong Xiong, Ao Zhang
Article
Chemistry, Multidisciplinary
Zhoulong Fan, Katherine L. Bay, Xiangyang Chen, Zhe Zhuang, Han Seul Park, Kap-Sun Yeung, K. N. Houk, Jin-Quan Yu
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Han Seul Park, Zhoulong Fan, Ru-Yi Zhu, Jin-Quan Yu
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Zhe Zhuang, Alastair N. Herron, Zhoulong Fan, Jin-Quan Yu
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Nelson Y. S. Lam, Zhoulong Fan, Kevin Wu, Han Seul Park, Su Yong Shim, Daniel A. Strassfeld, Jin-Quan Yu
Summary: This study summarizes key factors for achieving high selectivity at defined aryl positions by analyzing 119 structurally unique remote DTs, which are experimentally corroborated through the development of new aliphatic meta and para-selective DTs for electronically unbiased arenes. These empirical rules, summarizing key distance and geometric factors, are expected to be useful tools for the future development of site-selective arene C-H activation and other reactions relying on covalent/noncovalent DT-mediated remote regioselection.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Zhoulong Fan, Xiangyang Chen, Keita Tanaka, Han Seul Park, Nelson Y. S. Lam, Jonathan J. Wong, K. N. Houk, Jin-Quan Yu
Summary: This study presents two distinct directing templates that allow for the differentiation and functionalization of remote and similar positions on bicyclic aza-arenes. This strategy enables site-selective C-H olefination, alkynylation, and allylation reactions on quinoline-containing compounds, and can be performed in a modular fashion in different orders.
Article
Chemistry, Multidisciplinary
Zhoulong Fan, Shuai Zhao, Tao Liu, Peng-Xiang Shen, Zi-Ning Cui, Zhe Zhuang, Qian Shao, Jason S. Chen, Anokha S. Ratnayake, Mark E. Flanagan, Dominik K. Kolmel, David W. Piotrowski, Paul Richardson, Jin-Quan Yu
Review
Chemistry, Organic
Li-Rui Song, Zhoulong Fan, Ao Zhang
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)