Article
Chemistry, Multidisciplinary
Rupeng Qi, Chao Wang, Yumei Huo, Hongli Chai, Hongying Wang, Zijian Ma, Liangyu Liu, Rui Wang, Zhaoqing Xu
Summary: Asymmetric functionalization of C-H is a attractive strategy in asymmetric synthesis, and photoredox catalysis has emerged as an efficient way to synthesize organic compounds under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Shuai Liu, Nivesh Kumar, Frederic Robert, Yannick Landais
Summary: A visible-light-mediated intramolecular site-selective delta-C(sp3)-H bond arylation of aliphatic trifluoromethanesulfonamides was developed. The reaction proceeds through a radical cascade, involving the generation of a sulfonamidyl radical, 1,5-hydrogen atom transfer, formation of a delta-C-centered radical, and finally cyclization onto a neighboring thiopolyfluoroaryl moiety to provide thiochromanes. The cyclization process occurs via two distinct pathways depending on the substituent X ortho to the native C-S bond.
Article
Chemistry, Organic
Xinpeng Xie, Kaikai Qiao, Bing-ru Shao, Wenfeng Jiang, Lei Shi
Summary: Cross-dehydrogenative coupling is a powerful tool for constructing C-C and C-heteroatom bonds. In this study, a visible-light-mediated radical CDC of C(sp(3))-H/C(sp(3))-H and C(sp(3))-H/C(sp(2))-H was reported, guided by a phenyl radical and intermolecular hydrogen atom transfer process. This strategy enables the efficient coupling of inert C(sp(3))-H and C(sp(2))-H with alpha-N C(sp(3))-H of amines, showing good regioselectivities and yields. Mechanistic studies revealed that the EDA complex triggers an intermolecular HAT process.
Article
Multidisciplinary Sciences
Qian-Yu Li, Shiyan Cheng, Ziqi Ye, Tao Huang, Fuxing Yang, Yu-Mei Lin, Lei Gong
Summary: This study developed a simplified photochemical system using iron(III) halides as multifunctional reagents and air as a green oxidant to achieve the direct and selective coupling of benzenes with aliphatic hydrocarbons. The method showed high yields and commendable chemo-, site-selectivity, and demonstrated the potential of iron halides in sustainable synthesis.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Sheng-Yun Zhou, Ding Zhang, Xiao-Jie Liu, Jing-Hao Qin, Zheng-Li Fu, Shuang-Long Li, Fang-Jun Cai, Yang Li, Jin-Heng Li
Summary: A novel photoredox-catalyzed C(sp(3))-C(sp(3)) cross-coupling reaction between N-arylamines and cycloketone oxime esters has been achieved under mild conditions. The redox-neutral reaction shows good functional group tolerance and excellent regioselectivity without the need for additional base or ligand control. Furthermore, this approach has been successfully applied for the late-stage modification of short peptides and analogues.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Huamin Wang, Meng He, Yongli Li, Heng Zhang, Dali Yang, Masanari Nagasaka, Zongchao Lv, Zhipeng Guan, Yangmin Cao, Fengping Gong, Zhilin Zhou, Jingyun Zhu, Supravat Samanta, Abhishek Dutta Chowdhury, Aiwen Lei
Summary: A highly selective, environmentally friendly, and scalable electrochemical protocol for constructing alpha-acyloxy sulfides has been developed, utilizing the synergistic effect of self-assembly-induced C(sp(3))-H/O-H cross-coupling. This protocol demonstrates broad substrate scope, high regioselectivity, gram-scale synthesis, construction of complex molecules, and applicability to various nucleophiles. The pivotal role of substrate self-assembly has been confirmed through soft X-ray absorption technique and control experiments, contributing to the excellent compatibility and precise regioselectivity control in the electrochemical protocol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Qing-Qiang Min, Jia-Wen Yang, Meng-Juan Pang, Gui-Zhen Ao, Feng Liu
Summary: An efficient and general method for catalytic installation of azido and thiocyanato groups via remote C(sp(3))-H activation is described. The copper-catalyzed reaction proceeds through a cascade of single-electron transfer, favorable 1,5-hydrogen atom transfer, and C-N/C-S cross-coupling, providing distal azido and thiocyanato alkylamines. This reaction is applicable to various types of C(sp(3))-H functionalization and demonstrates excellent site-selectivity and functional-group compatibility.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Gongbo Liu, Nan Zheng, Xuelun Duan, Xinhao Sun, Wangze Song
Summary: We report for the first time a novel visible light-induced radical relay strategy to achieve thiolation of C(sp(3))-H with thioacids. This strategy offers metal-free and additive-free conditions, excellent atom economy, and high yields (up to 98%). The methodology shows good functional group tolerance, such as cyanos, halogens, or heterocycles, and can be further applied to the one-pot preparation of ketones from thioacids by a tandem photocatalytic radical coupling reaction and the Liebeskind-Srogl cross-coupling reaction.
Article
Chemistry, Organic
Biao Wang, Min-Jie Zhou, Qi-Lin Zhou
Summary: Here, we present a novel protocol for visible-light-induced α,γ-C(sp3)-H difunctionalization of piperidines. This redox-neutral, atom-economical protocol, which has a wide substrate scope and good functional group compatibility, offers a concise and practical method for constructing piperidine-containing bridged-ring molecules. Preliminary mechanistic studies indicate that the highly regioselective activation of the inert γ-C(sp3)-H bond of piperidines is achieved through a 1,5-hydrogen atom transfer reaction of a nitrogen radical generated in situ.
Article
Chemistry, Organic
Rafael D. C. Gallo, Marcelo Duarte, Amanda F. da Silva, Celso Y. Okada, Victor M. Deflon, Igor D. Jurberg
Summary: The new reaction utilizing aryldiazoacetates and 1,3-diketones under visible light promotes C-C bond insertions to form 1,4-dicarbonyl compounds with high yields and selectivities. This straightforward and practical transformation is tolerant to air and moisture, without the need for metal catalysts. Mechanistic studies suggest the involvement of a key cyclopropanol intermediate resulting from an intramolecular rearrangement.
Review
Chemistry, Multidisciplinary
Weisi Guo, Qian Wang, Jieping Zhu
Summary: This tutorial review summarizes the recent progress in remote functionalization of C-H bonds, with a focus on photoredox-catalyzed remote C-H functionalization.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Organic
Yan Du, Xiaoqiang Yu, Jing-Jing Tang, Yang Li, Jiangli Fan, Fei Li, Ming Bao
Summary: This study described a visible-light-driven Mn-catalyzed C(sp(3))-Hamidation of diphenylmethane derivatives with dioxazolones. These reactions occur without the need for an external photosensitizer and achieved satisfactory to good yields (up to 81%) under mild conditions. Mechanistic investigations revealed that the reaction proceeds through a Mn-acyl nitrene intermediate and H-atom abstraction is the rate-determining step. Computational studies showed that the decarboxylation of dioxazolone depends on the conversion of ground-state dioxazolone-bounding Mn species to quartet spin state via visible-light irradiation.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sumit, Devesh Chandra, Ankita Thakur, Ankit Kumar Dhiman, Upendra Sharma
Summary: In this study, a highly regioselective trifluoromethylthiolation of the unactivated C(sp(3))-H bond of 8-methylquinolines catalyzed by Rh(III) was explored, with good yields and high regioselectivity. The reaction conditions are also applicable for late-stage functionalization of natural molecules santonin and caffeine-substituted 8-methylquinoline.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhaofan Jue, Yahao Huang, Jiahui Qian, Peng Hu
Summary: An iron-catalyzed remote C(sp(3))-H amination of alcohols through 1,5-hydrogen atom transfer has been developed, providing a mild method to generate delta-C(sp(3))-N bonds from primary, secondary, and tertiary alcohols. The protocol demonstrates a wide substrate scope and good functional group tolerance.
Article
Chemistry, Multidisciplinary
Haoyuan Li, Sen Li, Huimin Hu, Runbo Sun, Meixia Liu, Anjun Ding, Xiaoyong Liu, Wenlin Luo, Zhengjiang Fu, Shengmei Guo, Hu Cai
Summary: A visible-light-induced radical/radical cross-coupling reaction of quaternary ammonium salts and Hantzschs via C-N and C-C bond cleavage is reported, leading to the formation of 1,2-diphenylethanes. The synthetic approach provides a moderate to good yield and offers a method for constructing C(sp(3))-C(sp(3)) bonds.
CHEMICAL COMMUNICATIONS
(2023)
