Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(18), P. 5259 - 5266
Published: Jan. 1, 2023
The origin of regio- and stereoselectivities NHC-catalyzed enantioselective radical reactions an enal a pyridinium salt has been explored via theory for the first time.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12300 - 12309
Published: April 24, 2024
Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(
Language: Английский
Citations
24
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Jan. 6, 2025
The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency
Language: Английский
Citations
4
Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 3137 - 3145
Published: Feb. 8, 2022
Diradical generation followed by radical–radical cross-coupling is a powerful synthetic tool, but its detailed mechanism has yet to be established. Herein, we proposed and confirmed new model named relayed proton-coupled electron transfer (relayed-PCET) for diradical generation, which could open door reactions. Quantum mechanics calculations were performed on selected carbene-mediated reaction designed model, the exact electronic structural changes during radical processes have been observed first time.
Language: Английский
Citations
57
Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(8), P. 2240 - 2269
Published: July 11, 2022
This Review examines parts per million (ppm) palladium concentrations in catalytic cross-coupling reactions and their relationship with mole percentage (mol %). Most studies chemistry have historically focused on the concentration ratio between (pre)catalyst limiting reagent (substrate), expressed as mol %. Several recent papers outlined use of "ppm level" an alternative means describing reaction systems. led us to delve deeper into literature assess whether is a practically useful descriptor catalyst quantities palladium-catalyzed reactions. Indeed, we conjectured that many could, unknowingly, employed low levels" (pre)catalyst, generally, what would spread ppm look like across selection reported vast array literature. In few selected examples, examined other metal systems for comparison palladium.
Language: Английский
Citations
46
ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(19), P. 11547 - 11556
Published: Sept. 8, 2022
Bicyclo[1.1.1]pentanes (BCPs) are of great interest to the agrochemical, materials, and pharmaceutical industries. In particular, synthetic methods access 1,3-dicarbosubsituted BCP-aryls have recently been developed, but most protocols rely on stepwise C–C bond formation via initial manipulation BCP core make electrophile or nucleophile followed by a second step (e.g., transition-metal-mediated cross-coupling step) form key BCP-aryl bond. Moreover, despite prevalence C–F bonds in bioactive compounds, one-pot, multicomponent directly functionalize [1.1.1]propellane corresponding fluoroalkyl scaffolds lacking. this work, we describe conceptually different approach diverse (fluoro)alkyl at low temperatures fast reaction times enabled an iron-catalyzed radical from readily available halides, [1.1.1]propellane, Grignard reagents. Further, experimental computational mechanistic studies provide insights into mechanism ligand effects nature formation. Finally, these used develop method rapidly versatile (difluoro)alkyl halides bisphosphine-iron catalysis.
Language: Английский
Citations
46
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)
Published: Feb. 18, 2022
Abstract We herein report the preparation of solid and salt‐stabilized silylzinc pivalates from corresponding silyllithium reagents via transmetalation with Zn(OPiv) 2 . These resulting organosilylzinc show enhanced air moisture stability unique reactivity in silylative difunctionalization alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl benzylsilylation alkenes has been developed, which provides an easy method to access silanes broad substrate scope wide functional group compatibility. Kinetic experiments highlight that OPiv‐coordination is crucial improve pivalates. Furthermore, late‐stage functionalizations druglike molecules versatile modifications products illustrate synthetical utility this protocol.
Language: Английский
Citations
44
Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)
Published: Dec. 23, 2022
Given the widespread significance of vicinal diamine units in organic synthesis, pharmaceuticals and functional materials, as well privileged molecular catalysts, an efficient practical strategy that avoids use stoichiometric strong oxidants is highly desirable. We herein report application ligand-to-metal charge transfer (LMCT) excitation to 1,2-diazidation reactions from alkenes TMSN
Language: Английский
Citations
42
Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(9), P. 847 - 857
Published: Aug. 21, 2023
Language: Английский
Citations
32
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4903 - 4912
Published: Feb. 12, 2024
Cross-electrophile couplings are influential reactions that typically require a terminal reductant or photoredox conditions. We discovered an iron-catalyzed reaction couples benzyl halides with disulfides to yield thioether products in the absence of and under The disclosed platform proceeds without sulfur-induced catalyst poisoning use exogenous base, supporting broad scope circumventing undesired elimination pathways. applied developed chemistry new mode disulfide bioconjugation, drug synthesis, gram-scale product derivatization. Lastly, we performed mechanistic experiments better understand stereoablative between two electrophiles. Disulfides benzylic thioethers imperative for biological pharmaceutical applications but remain severely understudied comparison their ethereal amino counterparts. Hence, expect this iron catalysis downstream be interest greater scientific community.
Language: Английский
Citations
16
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9404 - 9412
Published: March 20, 2024
The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.
Language: Английский
Citations
14