Review
Chemistry, Multidisciplinary
Clement Jacob, Bert U. W. Maes, Gwilherm Evano
Summary: Direct functionalization of C-H bonds is a fundamental transformation in organic synthesis, often relying on directing groups for activation. The development of transient directing groups strategy has revolutionized C-H bond functionalization, allowing for direct and selective introduction of functional groups onto various substrates.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Ashfaq Ahmad, Himangsu Sekhar Dutta, Mohit Kumar, Raziullah, Manoj Kumar Gangwar, Dipankar Koley
Summary: A palladium catalyzed directing group assisted cross-coupling reaction has been developed for the synthesis of β-arylethylamine derivatives. The method is applicable to a wide range of substrates and can tolerate the presence of various external additives.
Review
Chemistry, Multidisciplinary
Jayabrata Das, Wajid Ali, Debabrata Maiti
Summary: In this review, the development of C(sp3)-H activation is highlighted, including its origins, progression, and overcoming of limitations, to identify future research directions. The three main strategies for C(sp3)-H activation in aliphatic molecules are static directing group (DG) or template-assisted approach, transient DG (TDG) approach, and native functional group (NFG)-assisted approach. Each section provides a brief discussion on the evolution, functionalization type, advantages, and shortcomings of C(sp3)-H activation.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Organic
Guanghua Kuang, Dandan Liu, Xuerong Chen, Guangyuan Liu, Yang Fu, Yiyuan Peng, Hua Li, Yirong Zhou
Summary: A unified method for direct C4-H halogenation of indoles has been successfully achieved with the assistance of anthranilic acids as suitable transient directing groups. Exclusive site selectivity and good functional group tolerance were obtained using inexpensive N-halosuccinimides as halogen sources under mild conditions. The rich functional groups in the product allow for facile construction of a diversity of nitrogen-containing heterocycles via one-step late-stage derivations.
Article
Chemistry, Multidisciplinary
Joe Higham, James A. Bull
Summary: Transient directing groups (TDGs) combined with copper have been used for efficient C-H functionalization without additional steps for directing group introduction and removal. This method demonstrates high regioselectivity in the beta-C(sp(2))-H sulfonylation and gamma-(peri)-sulfonylation reactions of benzaldehydes and achieves through the use of catalytic beta-alanine and sulfinate salts, with copper fluoride serving as both the copper source and oxidant.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gang Liao, Tao Zhang, Liang Jin, Bing-Jie Wang, Cheng-Kai Xu, Yu Lan, Yu Zhao, Bing-Feng Shi
Summary: In this study, we investigated the directing ability of chalcogenoether motifs in Pd-catalyzed atroposelective C-H functionalization through experimental and DFT computational studies. The results showed that the thioether motif exhibited superior reactivity and enantioselectivity compared to the corresponding ether and selenoether. Notably, DFT calculations provided a predictive model for optimizing reaction conditions and interpreting the origin of enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ming-Shun Mei, Yanghui Zhang
Summary: A new approach for the synthesis of naphthalimides via a tandem reaction of o-methylbenzaldehydes and maleimides is developed in this work. The reaction involves Pd(II)-catalyzed benzylic C(sp(3))-H oxidation using an amino acid as the transient directing group and Diels-Alder reaction. The subsequent dehydration forms naphthalimides, allowing for easy access to a range of naphthalimides with a variety of substituents.
Article
Chemistry, Multidisciplinary
Yusuke Kuroda, Kyungho Park, Yuto Shimazaki, Rong-Lin Zhong, Shigeyoshi Sakaki, Yoshiaki Nakao
Summary: Herein, an iridium/aluminum cooperative catalytic system has been reported for the beta-selective C-H borylation of saturated cyclic amines and lactams. An enantioselective variant has also been achieved using chiral aluminum catalysts, resulting in high stereocontrol in the formation of C-B bonds. Computational studies suggest that the formation of a Lewis pair with the substrates is crucial for lowering the energy of the rate-determining reductive elimination step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Liam S. Fitzgerald, Miriam L. O'Duill
Summary: This review discusses strategies for efficient removal of directing groups, focusing on the widely used N,N-bidentate directing group 8-aminoquinoline. The limitations of these strategies and alternative approaches for challenging substrates are also discussed. The aim is to provide a comprehensive guide for chemists in academia and industry to harness the synthetic power of directing groups and remove them from final products.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yaohang Cheng, Yuhang He, Jie Zheng, Hui Yang, Jun Liu, Guanghui An, Guangming Li
Summary: The method developed utilizes Ru(II) catalysis to facilitate the synthesis of challenging difluoroalkylated aldehydes and ketones with para-selectivity.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
Yangyang Wang, Gaorong Wu, Xiaobo Xu, Binghan Pang, Shaowen Liao, Yafei Ji
Summary: This study develops a method for the direct arylation of aliphatic ketones via Pd-catalyzed beta-C(sp(3))-H bond functionalization using 2-(aminooxy)-N,N-dimethylacetamide as a novel transient directing group (TDG), resulting in moderate to good yields. The reaction is tolerant to abundant substrate of ketones and aryl iodides, expanding the applications of TDGs.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Hamad H. Al Mamari, Diana Al Kiumi, Tamadher Al Rashdi, Huda Al Quraini, Malak Al Rashdi, Sumayya Al Sheraiqi, Sara Al Harmali, Mohammed Al Lamki, Ahmed Al Sheidi, Asma Al Zadjali
Summary: The novel design-based removable N,O-bidentate directing group enabled efficient Ru-catalyzed C(sp(2))-H arylation using 4-aminoantipyrine as a cheap and commercially available starting material. The reaction exhibited good scope, good functional group tolerance, and decent yields.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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
Chemistry, Multidisciplinary
Yulu Zhou, Yizhou Qin, Qinggui Wang, Zuxiao Zhang, Gangguo Zhu
Summary: A traceless directing group strategy was developed to reverse the regioselectivity of radical addition, enabling a photocatalytic sulfonylcarbocyclization of terminal alkynes and providing an efficient method for the synthesis of cyclopentenes and indenes. Mechanistic experiments revealed a radical cascade pathway involving several key steps.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Organic
Bing Zu, Yonghong Guo, Jie Ke, Chuan He
Summary: This short review focuses on recent advances in utilizing cTDGs and NDGs for the synthesis of chiral molecules, highlighting the potential of this method and hoping to inspire further research in this area.
SYNTHESIS-STUTTGART
(2021)