An iron-catalyzed reductive ring-rearrangement reaction of bridged benzo[]oxocin-4-ones with Grignard reagents to produce bridged benzo[]oxocin-2-ols is reported. Mechanistic studies indicate that an iron redox catalysis cycle involving oxidative addition to the C-O bond by low-valence iron and β-methoxyl elimination as key steps operates in this reaction.
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Iron-Catalyzed Reductive Ring-Rearrangement Reaction of Bridged Benzo[]oxocin-4-ones with Grignard Reagents to Afford Bridged Benzo[]oxocin-2-ols.
Org Lett
March 2025
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.
An iron-catalyzed reductive ring-rearrangement reaction of bridged benzo[]oxocin-4-ones with Grignard reagents to produce bridged benzo[]oxocin-2-ols is reported. Mechanistic studies indicate that an iron redox catalysis cycle involving oxidative addition to the C-O bond by low-valence iron and β-methoxyl elimination as key steps operates in this reaction.
View Article and Find Full Text PDFMechanism and Selectivity of Iron-Catalyzed [4+2] Cycloadditions of Unactivated Dienes: A Computational Study.
J Phys Chem A
March 2025
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
The mechanisms of iron-catalyzed [4 + 2] cycloadditions of unactivated dienes were investigated using density functional theory calculations. The calculation results show that the reaction involves sequential key steps of an initial ligand exchange followed by oxidative coupling, isomerization to form a seven-membered ferracycle intermediate, and C-C reductive elimination to form the cyclohexene product. The C-C reductive elimination step is shown to be the rate-determining step of the catalytic cycle.
View Article and Find Full Text PDFIron-Catalyzed Dearomatizing Reductive Cyclization of Arenes.
Org Lett
February 2025
School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China.
An efficient iron-catalyzed intramolecular dearomatizing reductive cyclization of arenes has been developed. By employing FeBr as the catalyst, tripyridine as the ligand, and Mn powder as the reductant, a series of spiro-cyclohexadienes and dihydronaphthalenes were afforded in moderate to excellent yields with aryliodine-tethered benzyl -butyl carbonate or naphthalene derivatives as substrates. In addition, several synthetic transformations were conducted to demonstrate the utility of the reaction, and control experiments were carried out to gain insight into the mechanism.
View Article and Find Full Text PDFThe Progress of Reductive Coupling Reaction by Iron Catalysis.
Chem Rec
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College of Sciences Northeastern University, Shenyang, 110819, China.
The transition metal catalyzed coupling reaction has revolutionized the strategies for forging the carbon-carbon bonds. In contrast to traditional cross-coupling methods using pre-prepared nucleophilic organometallic reagents, reductive coupling reactions for the C-C bonds formation provide some advantages. Because both coupling partners are reduced in the final products using a stoichiometric amount of a reductant, this approach not only avoids the need to use sensitive organometallic species, but also provides an orthogonal and complementary access to classical coupling reaction.
View Article and Find Full Text PDFIron-catalyzed radical Markovnikov hydrohalogenation and hydroazidation of alkenes.
Nat Commun
August 2024
Organisch-Chemisches Institut, Universität Münster, Münster, Germany.
We herein report radical hydroazidation and hydrohalogenation of mono-, di- and trisubstituted alkenes through iron catalysis. The alkene moiety that often occurs as a functionality in natural products is readily transformed into useful building blocks through this approach. Commercially available tosylates and α-halogenated esters are used as radical trapping reagents in combination with silanes as reductants.
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