Article
Chemistry, Multidisciplinary
Benxiang Zhang, Jiayan He, Yi Li, Tao Song, Yewen Fang, Chaozhong Li
Summary: Acylphosphonates with the 5,5-dimethyl-1,3,2-dioxophosphinanyl skeleton have been developed as efficient intermolecular radical acylation reagents for cobalt-catalyzed Markovnikov hydroacylation of unactivated alkenes at room temperature. The protocol shows broad substrate scope and good functional group compatibility, providing satisfactory yields of branched ketones. The proposed mechanism involves Co-H mediated hydrogen atom transfer and subsequent trapping of alkyl radicals by acylphosphonates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Peng Wang, Honghai Zhang, Mingqi Zhao, Shuangshuang Ji, Lu Lin, Na Yang, Xingliang Nie, Jinshuai Song, Saihu Liao
Summary: A new method based on radical fluorosulfonylation has been developed for the synthesis of aliphatic sulfonyl fluorides from unactivated alkenes. This method can be applied to the late-stage modifications of natural products and peptides, as well as drug ligation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yong Xia, Kalipada Jana, Armido Studer
Summary: A new and practical strategy for remote site-selective desaturation of amides via radical chemistry is reported in this communication. The method utilizes N-allylsulfonylamide moiety as N radical precursor and shows potential synthetic utility by dehydrogenating natural product derivatives and drugs. The remote desaturation is achieved on different types of unactivated sp(3)-C-H bonds using commercially available methanesulfonyl chloride as reagent and a Cu/Ag-couple as oxidant.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Sheng-Qiang Lai, Bang-Yi Wei, Jia-Wei Wang, Wei Yu, Bing Han
Summary: A tunable photocatalytic method using ketoxime carbonates as reagents has been developed for anti-Markovnikov hydro- and aminooxygenation of unactivated alkenes. The reaction is initiated by N-O bond homolysis of ketoxime carbonates under visible-light photocatalysis, followed by generation of alkoxylcarbonyloxyl and iminyl radicals leading to carbon radical addition to alkenes. The carbon radical can either abstract a hydrogen atom to form hydrooxygenation product or be trapped by iminyl radical to yield aminooxygenation product.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Zhu Cao, Huihui Zhang, Xinxin Wu, Yahong Li, Chen Zhu
Summary: The research achieved the heteroarylation of unactivated aliphatic C-H bonds through radical-mediated heteroaryl migration, leading to a variety of heteroaryl-substituted aliphatic ketones. The method is applicable to O-/S-/N-containing heteroaryls and features mild C-C bond cleavage and good selectivity for tertiary C-H bonds.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Wen-Jun Yue, Craig S. Day, Adrian J. Brenes Rucinski, Ruben Martin
Summary: We present a modular catalytic technique that simplifies the preparation of gem-difluoroalkanes from unactivated sp3 precursors. This method exhibits simplicity, generality, and site selectivity, allowing for the functionalization of advanced intermediates and olefin feedstocks. Our strategy involves a cooperative interplay of halogen- and hydrogen-atom transfer, providing a new entry point to difluorinated alkyl bioisosteres of interest in drug discovery.
Article
Chemistry, Physical
Qiao Zhang, Simin Wang, Qian Zhang, Tao Xiong
Summary: A fascinating alkene remote migratory isomerization achieved by carbon radical addition to the C = C bond in alkenes via bimetallic catalysis has led to the expedient synthesis of alkenes bearing the distantly incorporated difluoromethylene (RCF2R') functionality. The retention of the C = C bonds in the products serves as a useful synthetic platform for accessing highly functionalized RCF2R'-containing molecules. Experimental studies have been conducted to provide insights into the potential mechanism.
Article
Chemistry, Organic
Rahul K. Shukla, Atul K. Chaturvedi, Subir Pal, Chandra M. R. Volla
Summary: In this study, a Pd(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes was demonstrated. The regioselectivity of the reaction was controlled by using a bidentate auxiliary and specific alkynes, leading to the formation of 1,6-dicarbonyl compounds through a cascade sequence.
Article
Chemistry, Multidisciplinary
Shin-Ho Kim-Lee, Pablo Mauleon, Ramon Gomez Arrayas, Juan C. Carretero
Summary: A novel dual Cu catalysis strategy based on a dynamic multiligand coordination pool is described, triggering cooperative polar/radical pathways in a single catalytic cycle. This strategy overcomes the reactivity issue in Cu-catalyzed carboboration, expanding the scope of the reaction and opening avenues to access stereodefined tetrasubstituted vinylboronates.
Article
Chemistry, Multidisciplinary
Chenxiao Qi, Guillaume Force, Vincent Gandon, David Leboeuf
Summary: A novel method for haloamidation is introduced in this paper, providing new building blocks for drug discovery. This method overcomes some limitations of traditional reactions and the reaction mechanism is deeply studied, which is expected to promote the development of more complex transformations in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Jie Shi, Li-Yun Guo, Qu-Ping Hu, Yu-Tao Liu, Qing Li, Fei Pan
Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.
Article
Chemistry, Organic
Zixian Yang, Yujia Shan, Jin-Tao Yu, Changduo Pan
Summary: An efficient protocol for the synthesis of ring-fused quinazolinone derivatives through hydroxyalkyl radical-initiated cyclization was established, providing a series of hydroxyl-containing quinazolinones in moderate to good yields. This metal-free reaction represents the first successful construction of ring-fused quinazolinones through radical C(sp(3))-H functionalization of simple alcohols and was applied in the synthesis of a Phaitanthrin A derivative.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Pan Zhou, Kaikai Niu, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: In this paper, a green, cost-effective, and eco-friendly electrochemical method is introduced for selective chlorosulfuration or chlorosulfoxidation of unactivated alkenes. This method offers the potential possibility for the preparation of high-value-added products in a more sustainable and greener manner.
Article
Chemistry, Physical
Laura Talavera, Robert R. A. Freund, Huihui Zhang, Matthew Wakeling, Mara Jensen, Ruben Martin
Summary: In this study, a novel Ni-catalyzed 1,1-difunctionalization reaction of unactivated terminal alkenes is disclosed, allowing for the incorporation of two different heteroatom motifs across an olefin backbone. This method provides a streamlined approach to the synthesis of alpha-aminoboronic acid derivatives from simple precursors and exhibits simplicity and generality across a wide range of coupling counterparts.
Article
Multidisciplinary Sciences
Yali Zhou, Xingjun Xu, Hongwei Sun, Guanyu Tao, Xiao-Yong Chang, Xiangyou Xing, Bo Chen, Chen Xu
Summary: This study reports effective platinum catalysts for hydroalkoxylation and hydroamination of unactivated alkenes, accommodating various alkene substitution patterns and providing a foundation for rational design of chiral catalysts through detailed mechanistic investigations.
NATURE COMMUNICATIONS
(2021)
