Tellurium(II)/Tellurium(III)-Catalyzed Cross-Dehydrogenative C?N Bond Formation

Article abstract of DOI:10.1002/anie.202015248

The Te^II/Te^III-catalyzed dehydrogenative C?H phenothiazination of challenging phenols featuring electron-withdrawing substituents under mild aerobic conditions and with high yields is described. These unexpected Te^II/Te

Full text of DOI:10.1002/anie.202015248

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Accepted Article
Title: Te(II)/Te(III) catalyzed cross dehydrogenative C─N bond
formation
Authors: Christopher Cremer, Monalisa Goswami, Christian Rank, Bas
de Bruin, and Frederic William Patureau
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Tellurium(II)/Tellurium(III)-Catalyzed Cross-Dehydrogenative C─N
Bond Formation
[
a]
[b]
[a]
[c]
Christopher Cremer, Monalisa Goswami, Christian K. Rank, Bas de Bruin, and Frederic W.
Patureau*[a]
Dedicated to Pierre H. Dixneuf for his scientific achievements.
[
a]
C. Cremer, C. K. Rank, Prof. Dr. F. W. Patureau
Institute of Organic Chemistry
RWTH Aachen University
Landoltweg 1, 52074 Aachen
E-mail: Frederic.Patureau@rwth-aachen.de
Dr. M. Goswami,
Spark904 BV,
Science Park 400, 1098 XH, Amsterdam
Prof. Dr. Bas de Bruin
[
[
b]
c]
Van’t Hoff Institute for Molecular Sciences,
University of Amsterdam
Science Park 904, 1098 XH, Amsterdam
Supporting information for this article is given via a link at the end of the document.
Abstract: The Te(II)/Te(III) catalyzed dehydrogenative C─H
phenothiazination of challenging phenols featuring electron
withdrawing substituents is herein described, under mild aerobic
conditions and with high yields. These unexpected Te(II)/Te(III)
radical catalytic properties were characterized by cyclic voltammetry,
EPR spectroscopy, kinetic experiments and DFT calculations.
metals to bypass unfavorable oxidation states while maintaining
catalytic activity. They can also actively take part in bond
breaking/forming events via hydrogen abstraction.[11,12] Thus, we
propose herein an unprecedented Te(II)/Te(III) catalysis
approach containing a bidentate, nitrogen-bridged redox non-
innocent ligand (Scheme 1), in the aim of unlocking new catalytic
properties.
Intermolecular cross dehydrogenative[1] C─N bond formation still
represents a relatively recent and underappreciated development
in the field of amination coupling reactions,[2] in spite of
pronounced step, atom, and redox economical advantages.[3]
These are moreover of particular sustainable character if air, or
2
O , can be successfully activated and utilized as the terminal
oxidant of the reaction.[4] Early examples are often metal
catalyzed, copper being one of the most often utilized metal
catalyst.[ Metal free halide catalysis has also been successfully
applied.[ Yet, the scope of such methods remain generally
limited. In this context of narrow applicability, the development of
new catalytic methods constitutes a strategic priority, especially
through the exploration of unusual catalytic elements and their yet
untapped properties. In view of our recent works focused on the
cross dehydrogenative phenothiazination of electron rich phenols,
affording access to valuable triarylamine materials (Scheme 1),[7]
we envisioned the idea of chalcogen catalysis, and in particular
tellurium catalysis,[8] in order to broaden the so far limited
substrate scope.[7] As a metalloid, tellurium combines properties
of both metal and non-metal elements. Therefore, it possesses a
low oxidation potential and various stable oxidation states, while
forming relatively stable C─Te bonds.[9]
5]
6]
In this context, recent developments in metal catalysis highlight
the use of ligands, which actively take part in the reaction via
electron transfer events. These ligands are so called “redox non-
innocent”.[10] Non-innocent ligands act in several ways. For
example, they can act as electron reservoir. This allows strategic
Scheme 1. Te(II/III)-catalyzed intermolecular cross dehydrogenative C─N bond
formation.
1
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In order to proceed with this objective, selenium and tellurium
azine derivatives were targeted as prospective catalysts. PSeZH
(PTeZH) was found significantly superior to the Se-catalyst
candidate (PSeZH). Moreover, while 5 mol% of PTeZH catalyst
loading provided encouraging results, 10 mol% was found optimal.
The optimized tellurium catalyzed conditions are shown in
Scheme 3 (product 3aa, 97% isolated).
(
phenoselenazine, X = Se) was easily accessed with a simple two
[
13]
step procedure from the literature (Scheme 2a).
PTeZH
(
phenotellurazine, X = Te) however proved slightly more
challenging. After testing and optimizing various retrosynthetic
approaches, we eventually established a route through 2,2’-
diiododiphenylamine (Scheme 2b). Indeed, the latter substance
could smoothly react with elemental tellurium under simple basic
conditions to afford PTeZH in 67% isolated yield (Scheme 2b).
This new method was found reliable and scalable, affording an
easy and serviceable route to the target tellurium metalloid based
heterocyclic catalyst. Once with the PSeZH and PTeZH catalyst
candidates in hand, we set out to optimize the tellurium catalysed
cross dehydrogenative phenothiazination of unprecedented and
typically challenging phenols featuring electron withdrawing
substituents (7 < pKa < 10). We finally selected and optimized a
mild O
2
mediated basic oxidation method, for a limited reaction
time of 3 hours.[
comparison to K
were also obtained with K
14]
K
2
4
HPO was found to be an optimal base in
3
PO
4
, NaHCO
3
, or AcOK, although good results
.[14] Importantly, the Te-catalyst
Scheme 2. Synthesis of PSeZH and PTeZH.
2
CO
3
Scheme 3. Te(II)/Te(III) catalyzed cross dehydrogenative C─N bond formation with challenging electron-neutral and electron-poor phenols, isolated yields,
predicted pKa values according to Scifinder ® accessed in November 2020.
2
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This Te-catalyzed reaction was found to tolerate a number of
unprecedentedly acidic phenols (pKa down to 7.5, entry 3ea,
7
3%), with high yields. Challenging functional groups such as
ketones, a pyridine and an aldehyde were moreover well tolerated
3ha, 3hb, 3he, 3pa, 3oa, 3qa). Importantly, control experiments
(
omitting the Te catalyst systematically led to very poor
conversions, thus highlight by contrast the strong catalytic role of
the Te(II) organometalloid PTeZH complex (Scheme 3). Moreover,
the non-catalyzed reaction (absence of PTeZH catalyst) does not
perform much better at longer reaction times. For example, the
un-catalyzed method afforded 3aa in only 66% yield after 24h
reaction time, versus 97% in 3h for the optimized Te-catalyzed
conditions. In some cases, the non-catalyzed reaction yielded
only traces of the expected coupling product (3ab, 3bb, 3bf, 3hb
<
2
5%). Thus, the use of these highly sustainable O based
reactions conditions require the presence of the PTeZH catalyst.
Finally, this Te(II)-catalyzed method allowed the straightforward
scale-up of the reaction without any loss of yield (3ia, pKa = 7.8,
0
+
Figure 1. CV plots (r.t.) in CH
2
Cl
2
, E°1/2ox values are reported versus Fc /Fc ,
86%), therefore demonstrating its robustness.
utilizing Fc* as an internal standard. E°1/2ox = +0.24, +0.22, +0.24, +0.08 V for
POZH (red), PSZH (green), PSeZH (blue), and PTeZH (pink), respectively.
In order to understand this remarkable catalytic effect, the cyclic
voltammetry (CV) plots of all four chalcogen congeners are
presented in Figure 1. The first three congeners (X = O, S, Se)
were found to have a similar oxidation potential (E°(1/2ox) = +0.24,
This oxidation potential difference for tellurium has important
consequences for its reactivity, as will be discussed thereafter.
Next, the radical character of each oxidized chalcogenazine
congener was investigated by electron paramagnetic resonance
(EPR) spectroscopy. The radical species were generated by
+0.22, +0.24 V, respectively). In contrast, the oxidation potential
of the largest congener (PTeZH, X = Te) deviates significantly
from the other three chalcogens, at only +0.08 V.
g-value
g-value
2.02
2.01
2
1.99
2.03
2.015
2
1.985
sim
exp
sim
exp
3
410 3420 3430 3440 3450 3460 3470
B [Gauss]
3300
3320
3340
B [Gauss]
3360
3380
g-value
g-value
2.03
2.015
2
2.03
2.015
2
1.985
sim
exp
sim
exp
3
380
3400
3420
3440
3460
3400
3420
3440
3460
3480
B [Gauss]
B [Gauss]



Figure 2. Experimental and simulated EPR spectrum of N-centered neutral radical POZ (top left), PSZ (top right), PSeZ (bottom left), and the radical cation
of PTeZH (bottom right), obtained by exposing the corresponding PxZH azine to air in benzene-d
were obtained with EasySpin, via the cwEPR GUI plugin, using the simulation parameters listed in Table S3 (see SI).
+
. Experimental parameters: see SI. The simulated spectra
6
[
15]
[16]
3
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bubbling air through a solution of POZH, PSZH, PSeZH and
PTeZH in benzene-d at room temperature. The corresponding
6
PTeZH is a good catalyst in this reaction because it combines a
significantly lower oxidation potential compared to PSZH (+ 0.08
V versus +0.22 V, respectively), such that it must oxidize first,
EPR profiles are shown in Figure 2. Interestingly, while we had
expected similar N-centered neutral radicals[17] for all four
investigated chalcogens, only the first three (X = O, S, Se) showed
an EPR signal that is compatible with an N-centered neutral
radical species PXZ (Figure 2). In contrast, phenotellurazine

together with a very reactive neutral N-centered radical (PTeZ ).
Indeed, the H-atom transfer (HAT) process was calculated to be

very favorable from PSZH to PTeZ . The later species therefore
[18]
serves as radical catalyst, which is generated from the in situ
+
(
PTeZH) delivered a very different EPR signal, which according
deprotonation of PTeZH , facilitated by the basic reaction
conditions and/or peroxide anions resulting from O reduction
to simulations and supporting DFT property calculations
2
+
corresponds to a (protonated) radical cation species: PTeZH .
This difference between tellurium and the other chalcogens
presumably arises from a lower oxidation potential (+0.08 V) and
subsequent weaker acidity of PTeZH+ compared to the other
three chalcomers (X = O, S, Se, E°(1/2ox) +0.22-0.24 V). Indeed,
one-electron oxidation of POZH, PSZH, and PSeZH apparently
(Scheme 5, see also SI). This process would thus increase the
rate of formation as well as the concentration of the key persistent

PSZ neutral radical species, which is a known intermediate in the
dehydrogenative phenothiazination reaction.[17] This favorable
HAT process would therefore lead to a reaction acceleration. Re-
oxidation of the PTeZH Te(II) catalyst would then occur again

+
+
leads to strongly acidified PxZH radical cations which
spontaneously deprotonate at nitrogen to the corresponding
persistent neutral radicals. In contrast, the (NPA) charge and spin
density of PTeZH+ are significantly shifted from N to Te (see SI,
Table S4).
towards the Te(III) PTeZH intermediate, thus closing the
catalytic cycle.
Next, we measured the relative initial rates of conversion (5 min.
reaction time) of the various chalcogenazines as N-substrates,
with common phenothiazine PSZH (X = S) as the reference (krel
). In those four parallel experiments, POZH was found to be the
fastest azine (krel = k /k = 4.4), and PTeZH the slowest (krel = 0.7,
=
1
X
S
Scheme 4a). In a competition set-up however (Scheme 2b),
POZH becomes 20 times faster, while PTeZH becomes circa 100
times ─ two orders of magnitude ─ slower than competing PSZH
(krel = 0.01). In the latter case moreover, the PSZH initial
conversion rate has been multiplied by 4 in comparison to the
non-catalyzed reaction (absence of PTeZH).
Scheme 5. The catalytic effect of PTeZH (X = Te) on the conversion of PSZH
(
X = S), proposed mechanism.
In conclusion, we have demonstrated that a Te(II) organometallic
complex could catalyze the dehydrogenative C─H
phenothiazination of challenging phenols baring electron
withdrawing substituents, with acidities as low as pKa = 7.5 (3ea,
73%). In all cases, the absence of Te(II) catalyst leads to
dramatically lower conversions. This unexpected catalytic effect
arises essentially from a combination of two important properties:
a lower oxidation potential of the PTeZH catalyst towards the
PTeZH radical cation and a significantly higher spin density at
the tellurium center compared to the sulfur based substrates. It is
thus probable that PTeZH will find further applications as radical
catalyst[18,19] for the development of innovative (radical catalyzed)
cross dehydrogenative couplings.
+
Scheme 4. Kinetic experiments, isolated yields, 5 min reaction time.
4
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9]
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5
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Entry for the Table of Contents
Insert graphic for Table of Contents here.
Te catalysis? The Te(II)/Te(III) catalyzed dehydrogenative C─H phenothiazination of challenging phenols is herein described, under
mild aerobic conditions and with high yields. These unexpected Te(II)/Te(III) radical catalytic properties were characterized by cyclic
voltammetry, EPR spectroscopy, kinetic experiments and DFT calculations.
Institute and/or researcher Twitter usernames: @patureaugroup @deBruingroup
6
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