Non-decarbonylative photochemical versus thermal activation of Bu4N[Fe(CO)3(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
Che-Hung Lin,Dominik Pursley,Johannes E. M. N. Klein,Johannes Teske,Jennifer A. Allen,Fabian Rami,Andreas Köhn,Bernd Plietker +7 more
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TBA[Fe] catalyzes the rearrangement of vinyl and arylcyclopropanes under thermal or photochemical conditions.Abstract:
The base metal complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofurans in good to excellent yields. Under photochemical conditions the reaction is performed at room temperature. Spectroscopic investigations show that the metal carbonyl catalyst is not decarbonylated. The best performance was observed at a wavelength of 415 nm. icMRCI+Q analysis of the excited singlet and triplet states of the [Fe(CO)3(NO)] anion was performed and used to calculate the vertical excitation energies which are in good agreement with the experimental data. CASSCF analysis indicates that the Fe center in all excited states of the ferrate becomes more electrophilic while adopting a distorted tetrahedral configuration. Both aspects have a positive synergistic effect on the formation of the initial π-complex with the incoming organic substrate.read more
Citations
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Automated Construction of Molecular Active Spaces from Atomic Valence Orbitals
TL;DR: The atomic valence active space technique is introduced, a simple and well-defined automated technique for constructing active orbital spaces for use in multiconfiguration and multireference electronic structure calculations that makes MR calculations easier to execute, easier to reproduce by any user, and simplifies the determination of the appropriate size of the active space required for accurate results.
Journal ArticleDOI
Synthetic applications of vinyl cyclopropane opening.
Marta Meazza,Hao Guo,Ramon Rios +2 more
TL;DR: An overview ofinyl cyclopropanes applications is given, focusing on the present century, for synthesis of cyclopentanes with good yields and sometimes excellent stereoselectivities.
Journal ArticleDOI
Iron‐Catalyzed Intramolecular C(sp2)−H Amination
Isabel T. Alt,Bernd Plietker +1 more
TL;DR: The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the direct intramolecular C-H amination of α-azidobiaryls and (azidoaryl)alkenes into the corresponding carbazoles and indoles, respectively, under mild conditions and with low catalyst loadings.
Journal ArticleDOI
Iron-Catalyzed Intramolecular Aminations of C(sp3)−H Bonds in Alkylaryl Azides
TL;DR: The nucleophilic iron complex Bu4 N[Fe(CO)3 (NO)] (TBA[Fe]) catalyzes the direct intramolecular amination of unactivated C(sp3 )-H bonds in alkylaryl azides, which results in the formation of substituted indoline and tetrahydroquinoline derivatives.
Journal ArticleDOI
Catalytic Enantioselective Cloke-Wilson Rearrangement.
Alesandere Ortega,Rubén Manzano,Uxue Uria,Luisa Carrillo,Efraim Reyes,Tomás Tejero,Pedro Merino,Jose L. Vicario +7 more
TL;DR: Racemic cyclopropyl ketones undergo enantioselective rearrangement to deliver the corresponding dihydrofurans in the presence of a chiral phosphoric acid as the catalyst, generating a carbocationic intermediate that subsequently undergoes cyclization.
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