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CoIII–Carbene Radical Approach to Substituted 1H‑Indenes
Version 2 2019-10-18, 17:40
Version 1 2016-07-08, 11:50
journal contribution
posted on 2019-10-18, 17:40 authored by Braja
Gopal Das, Andrei Chirila, Moniek Tromp, Joost N. H. Reek, Bas de BruinA new strategy for the catalytic synthesis of substituted 1H-indenes via metalloradical activation of o-cinnamyl N-tosyl hydrazones is presented, taking
advantage of the intrinsic reactivity of a CoIII carbene
radical intermediate. The reaction uses readily available starting
materials and is operationally simple, thus representing a practical
method for the construction of functionalized 1H-indene
derivatives. The cheap and easy to prepare low spin cobalt(II) complex
[CoII(MeTAA)] (MeTAA = tetramethyltetraaza[14]annulene)
proved to be the most active catalyst among those investigated, which
demonstrates catalytic carbene radical reactivity for a nonporphyrin
cobalt(II) complex, and for the first time catalytic activity of [CoII(MeTAA)] in general. The methodology has been successfully
applied to a broad range of substrates, producing 1H-indenes in good to excellent yields. The metallo-radical catalyzed
indene synthesis in this paper represents a unique example of a net
(formal) intramolecular carbene insertion reaction into a vinylic
C(sp2)–H bond, made possible by a controlled radical
ring-closure process of the carbene radical intermediate involved.
The mechanism was investigated computationally, and the results were
confirmed by a series of supporting experimental reactions. Density
functional theory calculations reveal a stepwise process involving
activation of the diazo compound leading to formation of a CoIII-carbene radical, followed by radical ring-closure to produce
an indanyl/benzyl radical intermediate. Subsequent indene product
elimination involving a 1,2-hydrogen transfer step regenerates the
catalyst. Trapping experiments using 2,2,6,6-tetra-methylpiperidine-1-oxyl
(TEMPO) radical or dibenzoylperoxide (DBPO) confirm the involvement
of cobalt(III) carbene radical intermediates. Electron paramagnetic
resonance spectroscopic spin-trapping experiments using phenyl N-tert-butylnitrone (PBN) reveal the radical
nature of the reaction.