Evidence for a one-electron mechanistic regime in dirhodium-catalyzed intermolecular C-H amination

Article abstract of DOI:10.1002/chem.201100708

Swift and energy efficient conversion of chemical feedstocks to pharmaceuticals and agrochemicals requires the development of new methods to add nitrogen functionality to unfunctionalized organic substrates. Dirhodium-catalyzed insertion of nitrene species into C-H bonds is a promising new method, the main drawback of which is the currently limited understanding of the catalytic mechanism. Herein, cyclic voltammetry and controlled potential electrolysis measurements have enabled us to solve many of the mechanistic mysteries of intermolecular C-H amination catalyzed by [Rh₂(esp) ₂] (esp=α,α,α′,α′-tetramethyl-1, 3-benzenedipropanoate). The primary result is that, in addition to a simple nitrene-transfer mechanism that dominates the early stages of the reaction, another mechanism is available that relies on sequential proton-coupled electron transfer steps. Whereas the nitrene-transfer mechanism requires the use of expensive, atom-inefficient oxidants, we show that simple one-electron oxidants such as Ce⁴⁺ may be used to achieve catalytic C-H amination via the one-electron mechanistic regime. Copyright

Full text of DOI:10.1002/chem.201100708

FULL PAPER
DOI: 10.1002/chem.201100708
Evidence for a One-Electron Mechanistic Regime in Dirhodium-Catalyzed
ꢀ
Intermolecular C H Amination
[
a]
Katherine P. Kornecki and John F. Berry*
Abstract: Swift and energy efficient
conversion of chemical feedstocks to
pharmaceuticals and agrochemicals re-
quires the development of new meth-
ods to add nitrogen functionality to un-
functionalized organic substrates. Dir-
hodium-catalyzed insertion of nitrene
species into CꢀH bonds is a promising
trolled potential electrolysis measure-
ments have enabled us to solve many
of the mechanistic mysteries of inter-
molecular CꢀH amination catalyzed by
trene-transfer mechanism that domi-
nates the early stages of the reaction,
another mechanism is available that
relies on sequential proton-coupled
electron transfer steps. Whereas the ni-
trene-transfer mechanism requires the
use of expensive, atom-inefficient oxi-
dants, we show that simple one-elec-
[Rh ACHTUNGNRTEUNG( esp) ] (esp=a,a,a’,a’-tetramethyl-
2 2
1,3-benzenedipropanoate). The primary
result is that, in addition to a simple ni-
4
+
new method, the main drawback of
which is the currently limited under-
standing of the catalytic mechanism.
Herein, cyclic voltammetry and con-
tron oxidants such as Ce
may be
Keywords: amination · catalysis ·
CꢀH activation · electrochemistry ·
used to achieve catalytic CꢀH amina-
tion via the one-electron mechanistic
regime.
rhodium
The controlled catalytic oxidative functionalization of ali-
Current mechanistic understanding of Rh -catalyzed CꢀH
2
phatic CꢀH bonds to produce new CꢀN bonds is a transfor-
amination stems from the work of Du Bois and co-work-
[2]
mative emerging method in organic synthesis that has the
potential to facilitate the synthesis of complex molecules in
ers. In initial work focusing on intramolecular amination
reactions that yield cyclic amine products, kinetic data were
found to be consistent with a mechanism in which the rate-
limiting step is the formation of an iminoiodinane, PhI=
[1,2]
an energy-efficient manner.
Although several transition
metals have been shown to accomplish oxidative CꢀH ami-
[3–12]
nation,
metal-metal bonded dirhodium complexes are
NSO R, from sulfamate ester and hypervalent iodine oxi-
3
the best catalysts for this process in terms of their efficiency
and selectivity, and are therefore utilized in a number of
dant PhI ACHTUNGTRENNUNG( OAc) (Equilibrium (I) in Scheme 1). Importantly,
2
radical clock experiments provided no evidence for the in-
[13,14]
[17]
synthetic applications.
Despite the successful application
volvement of radicals in these intramolecular reactions.
of dirhodium-catalyzed CꢀH aminations, a major drawback
In contrast to the intramolecular reactions described
above, catalytic intermolecular reactions are mechanistically
more complex, though they have a greater potential utility
in synthesis. In 2004, the Du Bois group made a major
breakthrough in intermolecular CꢀH amination through the
is that very little is known about the mechanism of the reac-
tion. The currently accepted mechanistic hypothesis for Rh2-
catalyzed CꢀH amination is highlighted in Regime A of
Scheme 1. In this mechanism, the Rh catalyst 1 intercepts a
2
nitrene from an iminoiodinane species, in our studies, PhI=
NTces (Tces=SO CH CCl ). The resulting Rh -nitrenoid
introduction of the new catalyst [Rh
2 ACHTUNGNTERNUNG( esp) ] (1) (Scheme 1);
2
its robustness is believed to be due to the chelating dicar-
3
2
3
2
[18]
species 1a is then responsible for the insertion of NTces
into a substrate CꢀH bond. Such a species has never been
observed or isolated, but is invoked in analogy to RhꢀRh=
boxylate ligand, esp, which disfavors ligand dissociation.
The mechanism of intermolecular CꢀH amination catalyzed
by 1, as investigated by Du Bois and co-workers, appears to
depend strongly on the concentration of CꢀH substrate. At
CR carbenoid intermediates in the corresponding Rh -cata-
2
2
lyzed carbine-transfer chemistry, for which convincing indi-
high substrate concentrations, a reaction profile similar to
that of intramolecular cyclizations is observed. However, at
[15,16]
rect evidence has been provided.
Here, we provide evi-
dence that a second mechanism, Regime B, which is based
on successive proton-coupled electron transfer (PCET)
lower CꢀH substrate concentrations, strong evidence for a
II,III
2
one-electron oxidized Rh
species of unknown composi-
steps, is operative in Rh -catalyzed intermolecular amina-
tions.
tion (hereafter referred to as A) as well as free radical de-
2
[19,20]
rived products are observed.
Importantly, product for-
mation occurs under both mechanistic regimes. The current
hypothesis put forth to explain these results is that CꢀH
[
a] K. P. Kornecki, Prof. J. F. Berry
Department of Chemistry, University of Wisconsin
II,II
amination arises by an exchange reaction of the Rh2 cata-
lyst 1 with iminoiodinanes to produce nitrenoid species 1a,
which inserts the nitrene equivalent into a CꢀH bond via a
1
101 University Avenue, Madison, WI 53706 (USA)
Fax : (+1)608-262-6143
E-mail: berry@chem.wisc.edu
[21]
concerted asynchronous transition state. Under the highly
Chem. Eur. J. 2011, 17, 5827 – 5832
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5827

We chose to examine the
amination of ethylbenzene with
H NTces as a model intermo-
2
lecular CꢀH functionalization
reaction for the work reported
here. [Rh2
a catalyst, and PhI ACHTUNGTERNNUNG( OAc) is
2
ACHTUNGTNERNUN(G esp) ] (1) is used as
2
employed as an oxidant, as
shown in Equation (1).
Under typical amination con-
ditions, the reactions proceed to
completion in roughly 48 h in
roughly 70% yield. A plot of
product concentration as
a
function of time (Figure 1) is il-
luminating. In the first 2 h,
there is an initial burst of reac-
tivity that results in conversion
of roughly 30% of the starting
material. After this preliminary
reactivity surge, the amination
product continues to form,
albeit at a slower rate. These
data are consistent with the two
rate regimes proposed by Du
[19]
Bois and co-worker.
More-
over, a significant amount (up
to 10% yield) of the acetoxylat-
ed byproduct, a-methylbenzyl
acetate, is identified in these re-
Scheme 1. Regime A: Currently hypothesized mechanism for C-H amination catalyzed by
1 (Tces=
SO CH CCl ). Regime B: Proposed observable Rh -amido intermediate in a mechanism that is driven by con-
3
2
3
2
secutive PCET steps to yield the same reactive Rh
each molecule for clarity.
2
-nitrenoid species. The second esp ligand is omitted from actions, suggesting the action of
acetoxy radicals, which have re-
oxidizing reaction conditions,
catalyst 1 is believed to be in
II,III
equilibrium with the Rh2
species A, which is postulated
to lead to decomposition of the
[20]
catalyst.
periments reported here show
that species A is indeed catalytically active.
However, the ex-
A goal of our research is to explore the fundamental coor-
dination chemistry and mechanistic underpinnings for the
activity of dirhodium catalysts such as 1, and we have re-
cently reported the preparation of the first metal–metal/
metal–ligand multiply bonded species analogous to 1a, a dir-
[
22]
uthenium nitride,
and its remarkable reactivity towards
[23]
proximal CꢀH bonds. Here, we report an investigation of
II,III
the electrochemical oxidation of [Rh ACHTUNGTRNEGNU( esp) ] to its Rh
2 2 2
II,III
form and show that a) Rh2
species are catalytically rele-
vant and b) intermolecular CꢀH functionalization can occur
without iminoiodinane-transfer reagents, validating the one-
electron-mediated mechanistic regime proposed as Regime
B in Scheme 1. Significantly, this work opens the door for
the future use of cheaper and more atom economical oxi-
dants in catalytic CꢀH amination.
2
Figure 1. Catalytic reactivity of 1 with PhI CAHTUNGTRENUNG( OAc) as the oxidant, record-
ed as a plot of product concentration versus time. Yields are based on
1
H NMR integration versus and internal 0.01m naphthalene standard.
5828
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ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5827 – 5832

Dirhodium-Catalyzed Intermolecular CꢀH Amination
FULL PAPER
ox
Figure 2. a) Conversion of 1 to 1 via CPE. b) UV/Vis spectrum of species A generated under catalytic reaction conditions. c) Shift observed upon addi-
ox
tion of 2,6-lutidine to an electrochemically generated solution of 1 with added sulfamate..
cently been exploited in the oxyamination of indoles report-
900 nm observed in situ for band 2 of A. We attribute the
[24]
ed by Dauban. Under the conditions of Equation (1), the
red species A is observed, and its electronic spectrum is
shown in Figure 2b.
imperfect isosbestic behavior in Figure 2a to the slow reac-
ox
tion of 1 with CH Cl to form 2 in small quantities.
2
2
It is well established that the energy of the Rh p* ! s*
2
II,II
2
Since product formation occurs in the presence of A, this
red species is potentially an intermediate in the reaction.
Thus, the identity of A is of paramount importance for a
complete understanding of the catalytic CꢀH amination re-
transition in Rh
species is strongly affected by the identi-
ty of axial ligands, so it is reasonable that band 2 in 1
ox
would also be sensitive to the nature of axially coordinated
[25]
ox
II,III
ligands. Thus, it is likely that 1 and A exist in the Rh2
action. We have used electrochemical one-electron oxida-
oxidation state, but differ in their axial ligands. To identify
ox
tion of 1 in CH Cl to address this problem. Cyclic voltam-
species A, we have treated 1 with potential catalytically
2
2
metry experiments show that 1 undergoes reversible one-
electron oxidation at E1/2 =1095 mV versus Ag/AgNO3.
Upon controlled potential electrolysis (CPE) of 1 at an ap-
relevant axial ligands. Addition of H NTces shifts band 2 by
2
only about 5 nm, which is consistent with coordination of
sulfamate ester, but inconsistent with the spectral features
of A.
plied potential of 1550 mV versus Ag/AgNO , the character-
3
istic Rh p* ! s* transition of 1 at 640 nm disappears, and
Considering the relative acidity of H NTces protons, it
2
2
ꢀ
is replaced by new bands at 500 and 810 nm, hereafter
called bands 1 and 2, respectively (Figure 2a), as the charge
necessary for one-electron oxidation is lost from the electro-
chemistry solution (calcd: 1.92 C vs. 1.95 C, observed experi-
mentally). Although the visible spectrum of this brilliant red
seemed reasonable to consider a deprotonated HNTces
ox
axial ligand. If a solution of electrochemically generated 1
is treated with 100 equivalents of H NTces and 100 equiva-
2
lents of the non-coordinating base 2,6-lutidine, band 2 in-
stantly shifts to lower energy (Figure 2c), closely mirroring
the spectrum of species A. This result suggests that species
A results from both one-electron oxidation and deprotona-
ox
solution, 1 , is qualitatively similar to that measured in situ
for A during catalytic amination (Figure 2b), band 2 in the
latter is shifted bathochromically by 80–100 nm to appear at
approximately 890–910 nm. Thus 1 and A show different
tion of H NTces coordinated to 1, and we therefore propose
2
ox
II,III
that A has the the Rh2
amido structure, 1b (Scheme 1).
spectroscopic characteristics and are therefore not the same
chemical species. Du Bois and co-worker have noted that 1
can be chemically oxidized in CH Cl by H NTces and PhI-
One reason that we suggest the structure 1b for species A is
its similarity to Cu –amido species that have been shown by
II
Warren and co-workers to be important intermediates in
2
2
2
[4]
II
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(OAc) to produce a catalytically inactive red species formu-
Cu-catalyzed CꢀH amination. The Cu –amido species are
2
[19]
lated on the basis of its mass spectrum as [Rh
A
H
U
G
R
N
N
(esp) Cl].
long-lived enough to be isolated and crystallographically
2
2
[3]
The chloride ligand is proposed to originate from CH Cl .
characterized. In contrast, we estimate the half-life of 1b
2
2
We report crystallographic characterization of such a chlo-
ride-ligated red species, which we generated by chemical ox-
idation of 1 with tris(4-bromophenyl)aminium hexachlor-
to be on the order of minutes under an inert atmosphere.
II,III
Similarly, the role of an Rh2
species as a tether for radi-
cal-like intermediates has been exploited by Doyle to ach-
[26]
oantimonate in the presence of H NTces and the base 2,6-
ieve hydrocarbon oxidation with tert-butyl hydroperoxide.
2
II,III
2
lutidine. This complex is actually a Rh
bis-axial chloro
In conjunction with the similarities to the above examples,
several pieces of chemical evidence support this structural
assignment of species A as 1b. First, though electrochemical
oxidation of 1 is possible, chemical oxidation of 1 requires
ꢀ
adduct, [Rh
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(esp) Cl ] (2, crystallographic data available
2
2
29]
2
[
from the CCDC ). Both axial sites are effectively blocked
by the presence of the chloro ligands, which explains the sta-
bility and catalytic inactivity of this species. However, the
UV/Vis spectrum of this inactive compound more closely re-
H NTces and a base to be present. Thus, 1 does not react
2
with PhI
ACHTUNGTNERNGNU( OAc) by itself, but it reacts with H NTces/PhI-
2 2
ox
sembles that of electrochemically generated 1 (band 2, l=
ACHTUNGTRENNUNG
(OAc) immediately to form 1b. Similarly, chemical oxida-
2
810 nm), and does not share the band at approximately
tion of 1 can be accomplished by using tris(4-bromophenyl)-
Chem. Eur. J. 2011, 17, 5827 – 5832
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5829

J. F. Berry et al.
aminium hexachloroantimonate only in the presence of
H NTces and 2,6-lutidine as described above. Compound 1
2
results of PhIAHCTUNGTRENNUNG
were observed in crude H NMR spectra.
2
1
does not react with aminium
oxidants by itself. Furthermore,
the electrochemical features of
1
are significantly altered by
the presence of H NTces and
2
2,6-lutidine, as evidenced by
cyclic voltammetry (Figure 3).
The double catalytic cycle in Scheme 1 can be used to ra-
tionalize the results presented here for catalytic intermolec-
ular CꢀH amination. In Scheme 1, the inner cycle (Regime
A) corresponds to the reactions that take place in the sub-
strate-rich regime of the reaction (the initial burst of reactiv-
ity), which are presumed to be faster than those of the outer
cycle, the substrate poor regime (Regime B). Regime A is
essentially unchanged from that deduced by Du Bois and
co-workers for intramolecular amination. Notably, we pro-
pose that Regime B proceeds via two sequential PCET
steps with the red species 1b as an observable intermediate,
and suggest that it converges with the substrate-rich mecha-
nism in the formation of the RhꢀRh=NTces nitrenoid spe-
cies (1a), which inserts -NTces into CꢀH bonds. Interesting-
2 2
Figure 3. a) Cyclic voltammogram (CV) of 1 in CH Cl . b) CV of 1 plus
H
2
NTces and ethylbenzene. c) CV of 1 plus H
2
NTces, ethylbenzene, and
ly, Regime B appears to be more robust over time than
Regime A.
2
,6-lutidine.
Several lines of evidence support the necessity and nature
of the proposed substrate-poor mechanism. In intramolecu-
lar amination, for which only the substrate-rich mechanism
appears to be operative, pre-formed iminoiodinanes (PhI=
NR species) quantitatively insert the -NR group into CꢀH
II,II
Addition of H NTces and 2,6-lutidine causes the Rh
Rh2
/
2
2
II,III
+
half-wave potential of 1 (E1/2 =0.80 V vs. Fc/Fc ) to
be approximately 200 mV more accessible than that for 1
without additives. The lowering of the redox potential in the
presence of a base is a signature feature of a PCET process.
Interestingly, when H NTces is added to an electrochemi-
cally generated solution of 1 in a 1:1 mole ratio, and a fur-
bonds in the presence of catalytic [Rh
2 ACHTUNGTNERNUN(G esp) ]. For intermo-
2
lecular aminations, however, similar experiments give only
[19]
about 33% of the CꢀH insertion product. When monitor-
2
ox
1
ing product conversion by H NMR spectroscopy using the
ther one equivalent of PhI
A
H
U
G
R
N
N
(OAc) is added in the presence
hypervalent iodine oxidant (Figure 1), the initial burst of ac-
tivity ends at a product concentration that corresponds to
about 30% yield of product by H NMR spectroscopy,
2
of excess ethylbenzene, the solution instantly becomes green
again, displaying the spectroscopic features of 1, suggesting
that one turnover occurs. When 2,6-lutidine is added in
1
nearly identical to the yield obtained with pre-formed PhIꢀ
NTces. Clearly, the substrate-rich mechanism in intermolec-
ular amination reactions becomes inactive after a period of
time for reasons that are currently unknown.
place of PhI
ACHTUNGTRENNUNG( OAc) , however, 1b is formed; further addition
2
of one equivalent of H O (aq.) returns the catalyst to the
2
2
II,II
Rh2
state. These results clearly establish 1b as a compe-
4
+
tent intermediate, showing that the pathway from 1b to 1
via the intermediacy of 1a is mechanistically viable
The yield for the reaction involving Ce fits nicely in this
context. In reactions like that given in Equation (1), the
overall yield from the reaction plateaus around 70%. If
Regime A contributes roughly 30% to product formation,
the remainder of the product formation must occur under
Regime B (40%). In the reaction described by Equation
(2), only Regime B is operable, and a 40% yield is obtained.
Clearly, Regime B exhibits an arrest at approximately 40%
conversion, and therefore future work in new catalyst design
must take into account the deficiencies of 1 in both mecha-
nistic regimes.
(
Scheme 1).
Our observation of the reduction of 1b to 1 in the pres-
ence of oxidant prompted us to test the mechanism pro-
posed for Regime B by performing catalytic CꢀH amination
using a one-electron oxidant. We were inspired by the
recent report of Pd-catalyzed CꢀH amination using Ce-
[27]
ACHTUNGTRENNUNG( SO ) by Yu and co-workers. This oxidant seemed advan-
4 2
tageous to us in that the sulfate groups could act as a base
for the necessary PCET steps. Thus, the reaction in Equa-
tion (2) was carried out, which is readily comparable to that
in Equation (1), under the analogous hypervalent iodine
conditions. CꢀH amination was observed on a quantitative
The robust nature of 1 has been attributed to its chelating
ligands, which may stabilize the one-electron oxidized inter-
mediate. However, there have been examples of dirhodium
compounds with chelating ligands that do not perform favor-
scale (40% yield) over 48 h, and notably, in contrast to the
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ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5827 – 5832

Dirhodium-Catalyzed Intermolecular CꢀH Amination
FULL PAPER
ably under amination conditions, but whose redox activity
nate (magic blue) (32 mg, 0.04 mmol) was dissolved in another 10 mL of
distilled dichloroethane. The magic blue solution was slowly added to the
reaction by using a cannula at 08C. A color change from green to brick
red was observed. The solution was filtered into a second Schlenk flask
through a medium filter frit to remove residual antimonate salts. The fil-
trate was then layered with hexanes and kept at ꢀ208C until crystals
formed.
[19]
has not been reported. This leads us to believe that Rh-
centered redox activity may be a necessary requirement for
mechanistic Regime B, another observation that may spur
new catalyst design.
The results reported here have several important implica-
4
+
tions for Rh -catalyzed CꢀH amination. First, we outline
Amination using Ce : A 25 mL Schlenk flask was charged with Ce-
(SO (398 mg, 1.2 mmol) and anhydrous ethylbenzene (3 mL) was
added by syringe. A second flask was charged with 1 (18 mg, 4 mol%),
NTces (137 mg, 0.6 mmol) and ethylbenzene (3 mL), the contents of
which were transferred to the slurry of Ce(SO ) by using a cannula.
2
A
H
U
G
R
N
U
G
4 2
)
features of a successful amination catalyst: the catalyst must
exhibit reversible, Rh-centered redox chemistry and must be
able to support an RhꢀRhꢀNHR linkage if Regime B is to
H
2
AHCTUNGTRENNUNG
4
2
be accessible. Second, the choice of oxidant may be ad-
dressed. Regime A strongly requires the use of expensive
After a few minutes in these conditions, the reaction mixture changed
color from green to red. After 48 h, the reaction was filtered to remove
cerium salts, rinsed with dichloromethane and concentrated. The amina-
tion product can be purified by column chromatography (9:1 hexanes/
[28]
and chemically promiscuous hypervalent iodine oxidants,
but this requirement is lifted in Regime B, opening the door
for the future development of methodology that utilizes
more environmentally friendly and atom economical oxi-
dants such as hydrogen peroxide, which is chemically com-
patible with the transformation from 1b to 1, but may not
be able to affect conversion of 1 to 1b. The improved selec-
tivity of Regime B is also promising, suggesting that the pos-
sibility of eliminating radical-derived side-products is now
1
EtOAc), yielding a yellow oil (40%). H NMR spectroscopy and ESI
mass spectrometry agree with characterization data published in the liter-
[
19]
ature.
Acknowledgements
We are grateful to the University of Wisconsin for financial support for
this project, as well as to the Chemical Sciences, Geosciences, and Biosci-
ences Division, Office of Basic Energy Sciences, Office of Science, U.S.
Department of Energy (DE-FG02–10ER16204).
4
+
an option, as we show to be the case when Ce is used.
Experimental Section
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[
[
[
[
[
[
[
2
3
1
Monitoring Equation (1) by H NMR spectroscopy: To a 10 mL Schlenk
flask charged with 1 (4.5 mg, 4 mol%), sulfamate (34 mg , 0.15 mmol),
and naphthalene (2.6 mg, 0.01m internal standard), dry [D
2 mL) was added into the reaction mixture , followed by the addition of
ethyl benzene (18.5 mL, 0.15 mmol) via microsyringe. Finally, PhI(OAc)
96 mg, 0.3 mmol) was added to the reaction—a color change to red is
generally observed at this point. A portion of the reaction solution was
transferred to a dry nitrogen-purged NMR tube, and spectra were col-
lected every 30 min for four hours from the same tube. A final spectrum
was collected after 40 h. Growth of the product methyl doublet at d=
.27 ppm is monitored.
Chemical oxidation to yield 2: Compound 1 (30 mg, 0.04 mmol) and
NTces (18 mg, 0.08 mmol) were added to a 25 mL Schlenk flask and
dried under vacuum. Freshly distilled dichloroethane (10 mL) was added
by using a cannula, followed by the addition of 2,6-lutidine (9 mL). In a
separate Schlenk flask, tris-(4-bromophenyl)aminium hexachloroantimo-
6
]benzene
(
5
074.
A
H
U
G
R
N
N
2
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(
1
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Chem. Eur. J. 2011, 17, 5827 – 5832
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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[
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[
Received: January 26, 2011
Published online: April 19, 2011
9
5832
www.chemeurj.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 5827 – 5832