Synthesis and Characterization of Donor-Acceptor Iron Porphyrin Carbenes and Their Reactivities in N-H Insertion and Related Three-Component Reaction.
J Am Chem Soc
; 145(9): 4934-4939, 2023 Mar 08.
Article
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| MEDLINE
| ID: mdl-36811995
ABSTRACT
Iron porphyrin carbenes (IPCs) have been extensively recognized as the reactive intermediates in various iron porphyrin-catalyzed carbene transfer reactions. While donor-acceptor diazo compounds have been frequently used for such transformations, the structures and reactivities of donor-acceptor IPCs are less explored. To date, no crystal structures of donor-acceptor IPC complexes have been reported, and therefore, the involvement of IPC intermediacy for such transformations lacks direct evidence. Here we report the synthesis and NMR characterization of several donor-acceptor IPC complexes from iron porphyrin and corresponding donor-acceptor diazo compounds. The X-ray crystal structure of an IPC complex derived from a morpholine-substituted diazo amide was obtained. The carbene transfer reactivities of those IPCs were tested by the N-H insertion reactions with aniline or morpholine as well as the three-component reaction with aniline and γ,δ-unsaturated α-keto ester based on electrophilic trapping of an ammonium ylide intermediate. Based on these results, IPCs were identified as the real intermediates for iron porphyrin-catalyzed carbene transfer reactions from donor-acceptor diazo compounds.
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MEDLINE
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Revista:
J Am Chem Soc
Año:
2023
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Article
País de afiliación:
China