Catalytic
Synthesis of N‑Heterocycles via Direct
C(sp3)–H Amination Using an Air-Stable Iron(III)
Species with a Redox-Active Ligand
Version 3 2017-04-05, 19:19
Version 2 2017-03-30, 15:22
Version 1 2017-03-28, 17:52
Posted on 2017-04-05 - 19:19
Coordination of FeCl3 to
the redox-active pyridine–aminophenol
ligand NNOH2 in the presence
of base and under aerobic conditions generates FeCl2(NNOISQ) (1), featuring
high-spin FeIII and an NNOISQ radical ligand. The complex has an overall S = 2 spin state, as deduced from experimental and computational data.
The ligand-centered radical couples antiferromagnetically with the
Fe center. Readily available, well-defined, and air-stable 1 catalyzes the challenging intramolecular direct C(sp3)–H amination of unactivated organic azides to generate a
range of saturated N-heterocycles with the highest turnover number
(TON) (1 mol% of 1, 12 h, TON = 62; 0.1 mol% of 1, 7 days, TON = 620) reported to date. The catalyst is easily
recycled without noticeable loss of catalytic activity. A detailed
kinetic study for C(sp3)–H amination of 1-azido-4-phenylbutane
(S1) revealed zero order in the
azide substrate and first order in both the catalyst and Boc2O. A cationic iron complex, generated from the neutral precatalyst
upon reaction with Boc2O, is proposed as the catalytically
active species.
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Bagh, Bidraha; Broere, Daniël L.
J.; Sinha, Vivek; Kuijpers, Petrus F.; P. van Leest, Nicolaas; Bruin, Bas de; et al. (2017). Catalytic
Synthesis of N‑Heterocycles via Direct
C(sp3)–H Amination Using an Air-Stable Iron(III)
Species with a Redox-Active Ligand. ACS Publications. Collection. https://doi.org/10.1021/jacs.7b00270
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AUTHORS (9)
BB
Bidraha Bagh
DB
Daniël L.
J. Broere
VS
Vivek Sinha
PK
Petrus F. Kuijpers
NP
Nicolaas P. van Leest
BB
Bas de Bruin
SD
Serhiy Demeshko
MS
Maxime A. Siegler
JI
Jarl Ivar van der Vlugt