Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: An efficient and straightforward strategy for the synthesis of isoquinolones through [4 + 2]-annulation was described. Through utilizing N-chlorobenzamides and vinyl acetate, isoquinolone derivatives were prepared in good yields with the presence of CoCp*(III) catalyst in a regioselective manner. Furthermore, the annulation reaction was diversified by using vinyl ketones. Mechanistic investigations such as deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Jiajie Li, Xin Xu, Zhenli Luo, Zhen Yao, Ji Yang, Xin Zhang, Lijin Xu, Peng Wang, Qian Shi
Summary: Cp*Rh(III)-catalyzed regioselective C-H annulation and alkenylation of 2-pyridones with terminal alkynes has been developed, providing efficient access to diversified compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Suresh Kumar Yadav, Masilamani Jeganmohan
Summary: A redox-neutral [4 + 2] annulation of N-chlorobenzamides/acrylamides with substituted alkenes using Co(III) catalyst at ambient temperature is demonstrated. The reaction provides pharmaceutically important 3,4-dihydroisoquinolinone derivatives in good yields, preserving the synthetically useful functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shanmugarajan Jothi Murugan, Masilamani Jeganmohan
Summary: This study describes an efficient and regioselective synthesis of isoquinolones by [4 + 2]-annulation of N-chlorobenzamides with vinyl acetate in the presence of CoCp*(III) catalyst. The annulation reaction was further diversified by using vinyl ketones, leading to the preparation of biologically valuable isoquinolone derivatives in good yields. Additionally, mechanistic investigations including deuterium labeling study and competition experiment were performed to support the proposed reaction mechanism.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Fei Zhao, Jing Chen, Jin Qiao, Yangbin Lu, Xiaoning Zhang, Hui Mao, Shiyao Lu, Xin Gong, Siyu Liu, Xiaowei Wu, Long Dai
Summary: This study achieved the synthesis of functionalized 1H-imidazo[1,5-a]indol-3(2H)-ones by utilizing electron-deficient alkynes as unconventional C-1 synthons in a redox-neutral rhodium(III)-catalyzed [4+1] annulation. The process exhibited high chemo- and regioselectivity, broad substrate scope, good tolerance of functional groups, moderate to high yields, and mild redox-neutral conditions, providing a robust method to access valuable 1H-imidazo[1,5-a]indol-3(2H)-ones.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Applied
Liming Zhang, Ru Zhao, Chunhui Liu, Zhaoyang Li, Jun-Long Niu, Hao-Ran Yang, Lijun Gao, Shuang-Liang Liu, Liming Zhou
Summary: The Rh(III)-catalyzed ortho alkylation of N-pyridylcarbazoles with nitroalkenes has been developed for the synthesis of a wide range of 2-(2nitroalkyl)carbazoles. Aromatic and aliphatic nitroalkenes both successfully participated in this alkylation reaction. The protocol also worked well with an indoline based substrate. Derivatization of the representative nitroalkane product was described.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Jing Liu, Deng-Yin Liu, Qian Yang, Yao-Fu Zeng, Xiao-Li Wang, Peng-Fei Wang, Yu-Jun Ruan, Miao-Miao Wen, Shang-Shi Zhang, Li-da Du, Xu-Ge Liu
Summary: A new catalytic system using allenyl derivatives bearing a directing-group assistant as a reaction promoter has been developed for the regioselective cyclization reaction of aromatic amides with allenes. This reaction exhibits mild reaction conditions, a broad substrate scope, and high functional-group compatibility, leading to the synthesis of valuable compounds containing isoquinolinone and pyrimido[1,6-a]indol-1(2H)-one skeletons.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Changduo Pan, Cheng Yuan, Dongdong Chen, Yuefeng Chen, Jin-Tao Yu
Summary: A new Rh(III)-catalyzed annulation of N-methyl arylhydrazines with iodonium ylides has been developed, providing a series of oxycycloalkyl-fused cinnolines in good yields under very simple reaction conditions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Shrikant M. Khake, Naoto Chatani
Summary: The Rh(III)-catalyzed reaction of aniline derivatives containing a pyrimidine directing group with vinylsilanes leads to the formation of C3-substituted indoline derivatives via a highly regioselective C-H activation/alkene cyclization cascade. Mechanistic experiments suggest that C-H bond cleavage is not the rate-determining step, but rather the reaction proceeds through the formation of a six-membered rhodacycle as a key catalytic species via pyrimidine-directed electrophilic ortho-C-H rhodation.
Article
Chemistry, Inorganic & Nuclear
Yatong Fu, Yu Li, Donghong Luo, Yibo Lu, Jiajun Huang, Ziyi Yang, Jian Lu, Yuan-Ye Jiang, Ju-You Lu
Summary: An efficient regioselective B(3,4)-H activation was achieved via a ligand strategy, leading to B(3)-monoacyloxylated and B(3,4)-diacyloxylated o-carboranes. Amino acid and phosphoric acid ligands were crucial for the success of the reaction, and the approach was compatible with a broad range of carboxylic acids.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Quannan Wang, Yu-Han Nie, Chen-Xu Liu, Wen-Wen Zhang, Zhi-Jie Wu, Qing Gu, Chao Zheng, Shu-Li You
Summary: In this study, an enantioselective C-H activation/annulation reaction catalyzed by CpRh(III) was reported for the efficient synthesis of planar chiral ferrocene-fused heterocyclic molecules. By finding suitable catalysts, products with high yields and excellent enantioselectivity were obtained. The proposed reaction mechanism was supported by experimental and computational studies.
Article
Chemistry, Organic
Anil Kumar, Vinayak Hanchate, Kandikere Ramaiah Prabhu
Summary: A regioselective synthesis of furanone-fused isoquinoline heterocycles was achieved in a single step using a Rh(III) catalyst, showing good regioselectivity with a wide range of alkynoates. The regioselectivity was guided by steric bulk at the C4 position of the 4-hydroxy-2-alkynoates. The synthetic utility was demonstrated with a model reaction scaled up to 1 g.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Lingheng Kong, Xi Han, Haohua Chen, Huaming Sun, Yu Lan, Xingwei Li
Summary: The regioselective coupling of NH indoles with diazo compounds using dimeric Rh(II) complexes as catalysts demonstrates selectivity towards C(6) or C(7) positions depending on the structure of the indoles. Mechanistic studies reveal that hydrogen-bonding directing effect plays a crucial role in determining the regioselectivity, with C-C bond formation proceeding through Friedel-Crafts-type attack. This work highlights the challenges and opportunities in controlling regioselectivity in reactions involving arene C-H bonds.
Article
Chemistry, Organic
Seohyun Shin, Kyusik Um, Gi Hoon Ko, Gi Uk Han, Dongwook Kim, Phil Ho Lee
Summary: This study presents a novel method for achieving regioselective B(4)-H allenylation of o-carboranes under ball-milling conditions, which cannot be achieved through conventional solution-based reactions.
Article
Chemistry, Organic
Saad Shaaban, Houhua Li, Christian Merten, Andrey P. Antonchick, Herbert Waldmann
Summary: The study reported a method for the catalytic enantioselective C-H functionalization for enantioenriched cyclopropylamines using a chiral RhJasCp complex. This method operates under mild conditions with high enantiocontrol, enabling access to cyclopropylamines with three contiguous stereocenters originating from the corresponding cyclopropenes.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Francesca M. Ippoliti, Joyann S. Barber, Yi Tang, Neil K. Garg
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Joyann S. Barber, Michael M. Yamano, Melissa Ramirez, Evan R. Darzi, Rachel R. Knapp, Fang Liu, K. N. Houk, Neil K. Garg
Article
Chemistry, Multidisciplinary
Evan R. Darzi, Joyann S. Barber, Neil K. Garg
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Multidisciplinary Sciences
Masao Ohashi, Cooper S. Jamieson, Yujuan Cai, Dan Tan, Daiki Kanayama, Man-Cheng Tang, Sarah M. Anthony, Jason V. Chari, Joyann S. Barber, Elias Picazo, Thomas B. Kakule, Shugeng Cao, Neil K. Garg, Jiahai Zhou, K. N. Houk, Yi Tang
Article
Chemistry, Organic
Joyann S. Barber, Dehuan Kong, Wei Li, Indrawan J. McAlpine, Sajiv K. Nair, Sylvie K. Sakata, Nicole Sun, Ryan L. Patman
Summary: In this study, a simple and robust procedure for the Rh(III)-catalyzed [4+2] cycloaddition of feedstock gases enabled through C-H activation is described. A diverse set of 3,4-dihydroisoquinolones and 3-methylisoquinolones have been prepared in good to excellent yields. The effects of using ethylene and propyne as coupling partners on C-H site selectivity have also been explored with a representative set of substrates and discussed in detail.
Article
Multidisciplinary Sciences
Hui-Qi Ni, Ilia Kevlishvili, Pranali G. Bedekar, Joyann S. Barber, Shouliang Yang, Michelle Tran-Dube, Andrew M. Romine, Hou-Xiang Lu, Indrawan J. McAlpine, Peng Liu, Keary M. Engle
NATURE COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Hui-Qi Ni, Phillippa Cooper, Shouliang Yang, Fen Wang, Neal Sach, Pranali G. Bedekar, Joyann S. Donaldson, Michelle Tran-Dube, Indrawan J. McAlpine, Keary M. Engle
Summary: In this study, we evaluated different ambiphilic organohalides for their participation in anti-selective carbocyclic or heterocyclic annulation with non-conjugated alkenyl amides under Pd-II/Pd-IV catalysis. By optimizing the reaction conditions, we developed protocols for the synthesis of various carbocyclic or heterocyclic compounds. We also demonstrated the reactivity of otherwise unreactive ambiphilic haloketones through Pd-II/amine co-catalysis. This method proceeds via a distinct Pd-II/Pd-IV mechanism, resulting in unique reactivity and selectivity patterns.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Multidisciplinary Sciences
Francesca M. Ippoliti, Nathan J. Adamson, Laura G. Wonilowicz, Daniel J. Nasrallah, Evan R. Darzi, Joyann S. Donaldson, Neil K. Garg
Summary: Small rings containing allenes are unconventional compounds that have been known since the 1960s. Despite having similar discovery time to benzyne and advantageous features, strained cyclic allenes have been underutilized in chemical synthesis. This study presents a concise total synthesis of lissodendoric acid A, a manzamine alkaloid, through the selective trapping of a short-lived cyclic allene intermediate. This synthetic approach efficiently constructs the azadecalin framework, resulting in a 12-step total synthesis with a 0.8% overall yield.
Article
Chemistry, Physical
Taeho Kang, Tugce G. Erbay, Kane L. Xu, Gary M. Gallego, Alexander Burtea, Sajiv K. Nair, Ryan L. Patman, Ru Zhou, Scott C. Sutton, Indrawan J. McAlpine, Peng Liu, Keary M. Engle
Article
Chemistry, Organic
Joyann S. Barber, Alexander Burtea, Michael R. Collins, Michelle Tran-Dube, Ryan L. Patman, Stephanie Scales, Graham Smith, Jillian E. Spangler, Fen Wang, Wei Wang, Shouliang Yang, JinJiang Zhu, T. Patrick Montgomery
Article
Chemistry, Organic
Francesca M. Ippoliti, Joyann S. Barber, Neil K. Garg