Article
Chemistry, Organic
Han Cao, Xuejing Liu, Fusheng Bie, Yijun Shi, Ying Han, Peng Yan, Michal Szostak, Chengwei Liu
Summary: The decarbonylative synthesis of thioethers from thioesters catalyzed by Rh is reported, showing excellent group tolerance to aryl chlorides and bromides without the need for phosphine ligands or inorganic bases. The methodology allows for gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chen-Xu Liu, Fangnuo Zhao, Qing Gu, Shu-Li You
Summary: This paper reports a new method for the enantioselective synthesis of planar chiral ferroceneformaldehydes through a rhodium(I)/phosphoramidite-catalyzed C-H bond arylation reaction. The method enables the efficient synthesis of enantiopure planar chiral ferroceneformaldehydes and their transformation into diverse functional groups.
ACS CENTRAL SCIENCE
(2023)
Article
Chemistry, Applied
Zhipeng Liu, Xinwei Hu, Can Yang, Haisheng Xie, Huanfeng Jiang, Wei Zeng
Summary: A new method was reported for the synthesis of 2-carbonylethylindole skeletons through Rh(III)-catalyzed Csp(2)-Csp(3) bond cleavage/carbonylethylation of alpha-indolyl alcohols with allylic alcohols. This transformation involved a cascade C-C bond cleavage/C-C bond formation, providing a novel approach for the construction of these complex skeletons.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Rohit Sarthi, Rohit Kumar, Tamanna Sharma, Upendra Sharma
Summary: In this study, a concise Rh(III)-catalyzed C(sp3)-H alkylation of 8-methylquinolines with oxabenzonorbornadiene scaffolds and other strained olefins was presented. The developed catalytic methodology exhibits key features such as the retention of the oxabenzonorbornadiene skeleton, broad substrate scope, and wide-ranging functional group tolerance. Mechanistic studies revealed that the reaction proceeds through a non-radical pathway, with the five membered rhodacycle serving as the key intermediate. This is the first report on the C(sp3)-H alkylation of 8-methylquinolines with strained oxabenzonorbornadiene scaffolds (with ring retention).
Article
Chemistry, Organic
Chittala Emmaniel Raju, Sridhar Balasubramanian, Galla Karunakar
Summary: An efficient synthetic method was developed for accessing isoquinoline-substituted isobenzofurans. By reacting substituted 1,5-diynes with isoquinoline N-oxides in the presence of a copper catalyst, moderate to excellent yields of isoquinoline-derived isobenzofurans were achieved. The reaction also yielded quinoline-substituted isobenzofurans when quinoline N-oxides and 1,5-diynes were used instead.
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Physical
Yang Liu, Wusheng Guo
Summary: This study reports the development of metal-free chemical processes using recyclable heterogeneous catalysts at ambient conditions, which is highly desired in pharmaceutical production. By using insoluble carbon nitride as a photocatalyst, pharmaceutically relevant organophosphorus(V) compounds were efficiently synthesized through the coupling of readily available starting materials. The photocatalyst exhibited wide functional group tolerance and the reactions were performed under visible-light irradiation at room temperatures. The recyclable g-CN photocatalyst could be easily separated and reused for multiple cycles without decreasing the reaction efficiency, indicating its great potential for larger-scale synthesis in industrial manufacturing.
Article
Chemistry, Multidisciplinary
Marius D. R. Lutz, Valentina C. M. Gasser, Bill Morandi
Summary: The development of transfer hydrogenation and borrowing hydrogen reactions has allowed for new possibilities in manipulating simple alcohols, while transfer hydrocarbylation can increase the versatility of tertiary alcohols. A novel catalytic method was reported for transfer hydrocarbylation, which involves a redox-neutral beta-carbon elimination mechanism. The experimental evidence supports the feasibility of this method for manipulating tertiary alcohols in catalysis.
Article
Chemistry, Multidisciplinary
Chao Zheng, Shu-Li You, Chen-Xu Liu, Pei-Pei Xie, Fangnuo Zhao, Quannan Wang, Zuolijun Feng, Haoyang Wang
Summary: Through comprehensive experimental and computational studies, the mechanism of Rh(I)-catalyzed C-H arylation has been elucidated, including the identification of each elementary step in the catalytic cycle and the structural characterization of key intermediates and transition states. This research provides a foundation for the rational design and development of challenging intramolecular reactions and successfully realizes the facile synthesis of planar chiral [m]ferrocenophanes, a class of rarely explored target molecules with strained structures and intriguing molecular topology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Aparna Tyagi, Neha Taneja, Jabir Khan, Chinmoy Kumar Hazra
Summary: In this study, a solvent- and transition-metal-free, iodine-catalyzed C-S bond formation method for the synthesis of beta-keto sulfones using easily accessible methyl ketones and sulfonyl hydrazides is reported. The study also includes the alpha-functionalization of beta-keto sulfones to synthesize beta-keto thiosulfones and alpha-iodo-beta-keto sulfones using iodine-catalyzed carbon-sulfide bond formation under solvent-free conditions and iodine-mediated carbon-iodine bond formation under aqueous conditions, respectively. The analytical studies and control experiments provide insights into a free-radical coupling strategy. Overall, this protocol is simple, scalable, and allows for a broad range of functional group tolerance, providing access to three functionalized organic scaffolds.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Amrita Das, Naoto Chatani
Summary: The Rh-catalyzed C-H alkylation of benzylamines with alkenes using a picolinamide derivative as a directing group was successfully achieved under flow conditions with both Rh(i) and Rh(ii) complexes serving as active catalysts. Deuterium labelling experiments indicated a potential carbene mechanism for this reaction. The flow process demonstrated advantages over batch processes in this study.
Review
Chemistry, Multidisciplinary
Ramandeep Kaur, Nidhi Jain
Summary: This review presents recent advances in inter- and intramolecular asymmetric sp(3) C-H bond functionalization utilizing ruthenium, rhodium, and iridium catalysts, and provides insights into the mechanistic aspects of these transformations.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Chemistry, Organic
Balu Ramesh, Masilamani Jeganmohan
Summary: An efficient and novel synthesis route for (E)-4-benzylideneisochroman-1-ones has been demonstrated using Ru(II) as a catalyst for the tandem cascade annulation of benzoic acids with alkylidenecyclopropanes. The reaction selectively delivers E-stereoselective 4-benzylideneisochroman-1-one derivatives in moderate to good yields, exhibiting completely different selectivity compared to previous methods. Furthermore, annulation with less-reactive beta C-H activation of vinylic acids with alkylidenecyclopropanes has been explored, leading to the synthesis of highly useful alpha-pyrone derivatives in the presence of an Rh(III) catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Demao Chen, Changfeng Wan, Yunyun Liu, Jie-Ping Wan
Summary: A facile and practical method for the synthesis of fused tricyclic pyrazolo[5,1-a]isoquinolines has been developed via the reactions of enaminones, hydrazine hydrochloride, and internal alkynes using Rh catalysis. The cascade reactions demonstrate the remarkable high-order bond functionalization, involving the transformation of aryl C-H, ketone C=O, and alkenyl C-N bonds in the enaminones. This study highlights the individual advantage of enaminones in the design of novel and efficient synthetic methods.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Eunjae Chung, Suho Kim, Amitava Rakshit, Pargat Singh, Jaewook Park, Taejoo Jeong, In Su Kim
Summary: In this study, the rhodium(III)-catalyzed C8-spiroannulation of 1-aminonaphthalenes with maleimides is investigated. The resulting C8-alkenylated 1-aminonaphthalenes can further react with nucleophilic 1-amino groups through intramolecular aza-Michael reaction, leading to the formation of spirofused tetracyclic frameworks. This method demonstrates a broad substrate scope and compatibility with various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
