Article
Chemistry, Applied
Juan Diego Pizarro, Lucia Moran-Gonzalez, Ivan Gonzalez-Fernandez, Feliu Maseras, Manuel R. Fructos, Pedro J. Perez
Summary: Copper catalysts containing ADAP ligand selectively functionalize unprotected indoles at the C3-H position through carbene transfer, without altering the N-H bond. Mechanistic studies, including DFT calculations, propose two competitive pathways that do not involve the formation of cyclopropane intermediates, contrasting with previous reports.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Alex Diaz-Jimenez, Roger Monreal-Corona, Albert Poater, Maria Alvarez, Elena Borrego, Pedro J. Perez, Ana Caballero, Anna Roglans, Anna Pla-Quintana
Summary: The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp(3))-H bond has been achieved for the first time during a silver-catalyzed carbene/alkyne metathesis (CAM) process, leading to the synthesis of a new family of benzoazepines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Ximei Zhao, Guanghui Wang, A. Stephen K. Hashmi
Summary: Carbene B-H insertion reactions, including free and metal carbene insertion into B-H bonds, have made significant advances in recent years. The development of this chemistry complements existing C-B bond formation strategies in terms of substrate scope, selectivity, and product diversity. Notably, catalytic enantioselective carbene B-H insertion reactions enable easy access to important chiral organoboron compounds.
Review
Chemistry, Multidisciplinary
Neha Jha, Nandkishor Prakash Khot, Manmohan Kapur
Summary: The past decade has seen significant advancements in transition-metal-catalyzed C-H bond activation and carbene migratory insertion reactions, facilitating the construction of diverse arene/heteroarene scaffolds. Various transition-metal catalysts are utilized for easy access to substituted heterocycles, with key mechanistic pathways involving C-H activation, diazo insertion, and subsequent coupling reactions.
Article
Chemistry, Multidisciplinary
Dong -Kai Wang, Liu-Bin Li, Fa-Liang Liu, Hui Qiu, Jiao-Zhe Li, Jianfeng Zhang, Chao Deng, Wen-Ting Wei
Summary: This study presents a novel method for the construction of all-carbon quaternary centers, specifically those with an alkyne-substituted framework, using a Fe-catalyzed formal insertion of diazo compounds into C(sp)-C(sp(3)) bonds of propargyl alcohols under mild conditions.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Ming-Yao Huang, Shou-Fei Zhu
Summary: In comparison to common carbene insertion reactions, the overlooked uncommon carbene insertion reactions have been gaining more attention recently for their synthetic potential. The perspective reviews the history and latest advances of uncommon carbene insertion reactions, discusses their potential applications and challenges, and provides an outlook for this promising field.
Article
Chemistry, Multidisciplinary
Satabdi Bera, Aniruddha Biswas, Rajarshi Samanta
Summary: Researchers focus on developing methods for synthesizing nitrogen-containing heterocycles, with a prominent strategy being regioselective C-H bond functionalizations through migratory insertion of metal-carbenes and nitrenes. This method can be used to construct various functionalized nitrogen heterocycles.
Article
Chemistry, Multidisciplinary
Ziyong Li, Ying Chen, Chuang Wang, Guangyang Xu, Ying Shao, Xinhao Zhang, Shengbiao Tang, Jiangtao Sun
Summary: The atroposelective synthesis of biaryl atropisomers via asymmetric C(sp(2))-H bond insertion reaction of arenes under rhodium catalysis has been achieved, providing moderate to excellent yields with good enantiomeric ratios. Further investigation suggests that this type of axially biaryl scaffold may have promising potentials in developing novel chiral ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Lin-Yu Jiao, Zi-Hui Ning, Xiao-Mei Yin, Qian Hong, Shanshan Liu, Xiao-Xun Ma
Summary: A efficient and convenient method for rhodium(III)-catalyzed chelation-assisted ortho-selective carbon-hydrogen bond alkylation of phenols using readily available diazocarbonyl compounds as the alkyl source has been described. The migratory carbene insertion is the key step for this carbenoid coupling transformation, resulting in a wide range of alkylated products and the release of nitrogen gas as the sole byproduct. This protocol offers exclusive regioselectivities, moderate to excellent chemical yields, and good functional group tolerance.
CATALYSIS COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Bo Liu, Ming-Hua Xu
Summary: This study presents a new version of asymmetric carbene C-H insertion reaction using a rhodium(I) catalyst and chiral ligand, enabling efficient synthesis of a variety of chiral products at room temperature with excellent enantioselectivities. The synthetic utility of this method is demonstrated through the facile synthesis of a novel cannabinoid CB1 receptor ligand, suggesting potential for the development of therapeutically exploitable cannabinoid receptor type ligands in medicinal chemistry.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Balu D. Dherange, Patrick Q. Kelly, Jordan P. Liles, Matthew S. Sigman, Mark D. Levin
Summary: This study presents a reaction for selectively generating 3-arylpyridine and quinoline motifs by inserting aryl carbynyl cation equivalents into pyrrole and indole cores. The use of α-chlorodiazirines as thermal precursors allows for a modification of the traditional protocol to directly afford these compounds. Selectivity based on pyrrole substitution patterns is examined, with a predictive model proposed based on steric effects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Hisanori Nambu, Ryoya Amano, Takafumi Tamura, Takayuki Yakura
Summary: This study describes the dirhodium(II)-catalyzed intramolecular insertion of aryldiazoacetates into unactivated primary C-H bonds. The reaction shows high selectivity and provides a direct route to 2-unsubstituted indane-1-carboxylates and specific isomers with ortho-substituted groups. Furthermore, a chemoselective C-H insertion reaction of aryldiazoacetate with a 1-oxyethyl substituent is achieved using a specific protecting group.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Benjamin D. Bergstrom, Amy T. Merrill, James C. Fettinger, Dean J. Tantillo, Jared T. Shaw
Summary: This article reports the first synthesis methods of Panowamycins and their epimers, and reveals the previous structural misassignment of panowamycin A and veramycin F. The researchers achieved these synthesis methods through dirhodium-catalyzed C-H insertion reactions and Wacker oxidation, avoiding the use of protecting groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ana Amic, Dejan Milenkovic, Zoran Markovic, Denisa Cagardova, Jaime Rodriguez-Guerra Pedregal, Jasmina M. Dimitric Markovic
Summary: The kinetics and thermodynamics of phenolic O-H and C-ring C-H bond breaking in dihydrokaempferol, a natural flavonoid compound, were investigated using a density functional based approach. The study found that the 4'-OH phenolic hydrogen is involved in the inactivation of a hydroperoxyl radical (OOH), while the hydrogen atom transfer mechanism is responsible for C-H bond cleavage.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Anabel M. Rodriguez, Jorge Perez-Ruiz, Francisco Molina, Ana Poveda, Raul Perez-Soto, Feliu Maseras, M. Mar Diaz-Requejo, Pedro J. Perez
Summary: This paper describes the direct functionalization of Si-H bonds using nitrene insertion methodology. It was found that a copper(I) complex with a trispyrazolylborate ligand can catalyze the transfer of a nitrene group from PhI=NTs to the Si-H bond of silanes, disilanes, and siloxanes, leading to the exclusive formation of Si-NH moieties. The process is also tolerant of other functionalities in the substrate, such as multiple C-H bonds and alkynyl and vinyl moieties directly bonded to the silicon center. Density functional theory calculations provide a mechanistic interpretation involving Si-H homolytic cleavage and subsequent rebound to the Si-centered radical.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Organic
Jiun-Le Shih, Po-An Chen, Jeremy A. May
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Organic
Truong N. Nguyen, Thien S. Nguyen, Jeremy A. May
Article
Chemistry, Organic
Santa Jansone-Popova, Jeremy A. May
Review
Chemistry, Organic
Po-An Chen, Jeremy A. May
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2016)
Article
Chemistry, Organic
Truong N. Nguyen, Jeremy A. May
Article
Chemistry, Inorganic & Nuclear
Hiroyuki Hattori, Dong Hyun Koo, Jeremy A. May
Article
Chemistry, Organic
Jeremy A. May, Thien S. Nguyen, Truong N. Nguyen, Phong Q. Le, Po-An Chen, Ravikrishna Vallakati
Article
Chemistry, Organic
Truong N. Nguyen, Jeremy A. May
TETRAHEDRON LETTERS
(2017)
Article
Chemistry, Multidisciplinary
Jiun-Le Shih, Santa Jansone-Popova, Christopher Huynh, Jeremy A. May
Article
Chemistry, Organic
Truong N. Nguyen, Jeremy A. May
Review
Biochemistry & Molecular Biology
Truong N. Nguyen, Po-An Chen, Krit Setthakarn, Jeremy A. May
Article
Chemistry, Organic
Qinxuan Wang, Jeremy A. May
Article
Chemistry, Organic
Qinxuan Wang, Jiun-Le Shih, Ka Yi Tsui, Croix J. Laconsay, Dean J. Tantillo, Jeremy A. May
Summary: This study investigated various types of Huisgen cyclization or nitrene/carbene alkyne cascade reactions with different types of termination. Accessible nitrene precursors were evaluated, and carbonazidates were found to be the only effective initiators. The reaction outcome can be influenced by solvents, terminal alkynyl substituents, and catalysts. The mechanism was studied both computationally (using density functional theory) and experimentally, revealing relevant intermediates and plausible reaction pathways.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Clayton P. Donald, Amy Boylan, Truong N. Nguyen, Po-An Chen, Jeremy A. May
Summary: The (IPr)GaCl3/AgSbF6, AgSbF6, and GaCl3 catalysts were found to efficiently catalyze the substitution of the hydroxyl group of secondary and tertiary propargylic alcohols with organoboronic acids via C-C bond formation, and GaCl3 catalyst effectively synthesized all-carbon quaternary propargylic centers. These catalysts demonstrated the ability to perform substitutions at carbons bearing alkyl substituents, a capability that was lacking in other systems. The study showed that highly hindered carbon stereocenters, including quaternary centers bearing doubly ortho-substituted aryl rings, could be accessed efficiently using this method.
Article
Chemistry, Organic
Jirong Luo, Jeremy A. May
Summary: Cannabinoid research relies on synthesizing derivatives for structure-activity relationship studies. (-)-Delta(9)- Tetrahydrocannabinol and cannabidiol were successfully synthesized via a seven-step reaction using a novel ambiphilic trifluoroborate in a tandem enantioselective conjugate addition/enolate alkylation annulation. A new class of alkenyl and aryl ambiphilic trifluoroborates were also synthesized, demonstrating great compatibility with various functional groups, high yields, and excellent enantio- and diastereoselectivity. Furthermore, a novel benzo-fused cannabinoid analogue and tandem quaternary stereocenter-containing reaction products were synthesized with good to excellent enantioselectivity.
