Selective benzylic C–H monooxygenation mediated by iodine oxides

Article abstract of DOI:10.3762/bjoc.15.55

A method for the selective monooxdiation of secondary benzylic C–H bonds is described using an N-oxyl catalyst and a hypervalent iodine species as a terminal oxidant. Combinations of ammonium iodate and catalytic N-hydroxyphthalimide (NHPI) were shown to be effective in the selective oxidation of n-butylbenzene directly to 1-phenylbutyl acetate in high yield (86%). This method shows moderate substrate tolerance in the oxygenation of substrates containing secondary benzylic C–H bonds, yielding the corresponding benzylic acetates in good to moderate yield. Tertiary benzylic C–H bonds were shown to be unreactive under similar conditions, despite the weaker C–H bond. A preliminary mechanistic analysis suggests that this NHPI-iodate system is functioning by a radical-based mechanism where iodine generated in situ captures formed benzylic radicals. The benzylic iodide intermediate then solvolyzes to yield the product ester.

Full text of DOI:10.3762/bjoc.15.55

Selective benzylic C–H monooxygenation mediated by
iodine oxides
Kelsey B. LaMartina1, Haley K. Kuck1, Linda S. Oglesbee1, Asma Al-Odaini1
and Nicholas C. Boaz*1,2,3
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2019, 15, 602–609.
1Department of Chemistry and Physics, North Central College, 30 N.
Brainard Street, Naperville, IL 60540 USA, 2Department of Chemistry,
Frick Chemical Laboratory, Princeton University, Washington Road,
Princeton, NJ 08544 USA and 3Permanent address: Department of
Chemistry, North Central College, 30 N. Brainard Street, Naperville, IL
60540 USA; phone: +1-630-637-5187.
doi:10.3762/bjoc.15.55
Received: 13 December 2018
Accepted: 19 February 2019
Published: 05 March 2019
Associate Editor: C. Stephenson
Email:
Nicholas C. Boaz* - ncboaz@noctrl.edu
© 2019 LaMartina et al.; licensee Beilstein-Institut.
License and terms: see end of document.
* Corresponding author
Keywords:
acetoxylation; benzylic; iodate; NHPI; oxidation; radical
Abstract
A method for the selective monooxdiation of secondary benzylic C–H bonds is described using an N-oxyl catalyst and a hyperva-
lent iodine species as a terminal oxidant. Combinations of ammonium iodate and catalytic N-hydroxyphthalimide (NHPI) were
shown to be effective in the selective oxidation of n-butylbenzene directly to 1-phenylbutyl acetate in high yield (86%). This
method shows moderate substrate tolerance in the oxygenation of substrates containing secondary benzylic C–H bonds, yielding the
corresponding benzylic acetates in good to moderate yield. Tertiary benzylic C–H bonds were shown to be unreactive under similar
conditions, despite the weaker C–H bond. A preliminary mechanistic analysis suggests that this NHPI-iodate system is functioning
by a radical-based mechanism where iodine generated in situ captures formed benzylic radicals. The benzylic iodide intermediate
then solvolyzes to yield the product ester.
Introduction
The ability to install C–O functionality with high selectivity benzylic alcohols, aryl ketones, and aryl carboxylic acids,
into a C–H bond is a challenge to synthetic organic chemists. which are useful chemical building blocks. Strategies that
Importantly, this transformation allows for the creation of prevent over-oxidation at the target site are particularly useful.
value-added products from hydrocarbon feedstocks. Benzylic
positions are a prevalent example of a functionality whose rela- Given the value of the oxidized benzylic products, a substantial
tively weak C–H bonds (≈80–90 kcal/mol) make selective func- amount of effort has been expended in developing ways to
tionalization possible [1,2]. The installation of oxygen function- selectively transform benzylic C–H bonds to C–O functionali-
ality at benzylic C–H bonds allows for the production of ties. Traditionally, this has been accomplished via the treatment
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Beilstein J. Org. Chem. 2019, 15, 602–609.
of a substrate containing benzylic C–H bonds with acidic sodi- formed from species such as NHPI are well studied H-atom
um dichromate or basic potassium permanganate [3-5]. More abstraction catalysts often used in the functionalization of
recent examples have used metal coordination complexes as hydrocarbons [41]. Building upon the ability to selectively
catalysts for oxidation [6-20]. Additionally, transition metal- acetoxylate the tertiary position of adamantane, we sought to
based complexes are widely used in industrial processes as apply this approach to the selective acetoxylation of benzylic
promoters of autoxidation in the functionalization of benzylic C–H bonds. As shown in Figure 1, the use of ammonium iodate
C–H bonds of aryl alkanes, such as in the synthesis of tereph- in combination with an NHPI-type catalyst yielded efficient
thalic acid from p-xylene [21].
benzylic oxidation of n-butylbenzene (1a) to 1-phenylbutyl
acetate (3a) with a concomitant reduction of iodate to iodine.
Metal-free oxidants have been used in benzylic C–H to C–O
functionalization. Specifically, the use of hypervalent iodine
oxidants to mediate benzylic C–H oxidation is one area experi-
encing a surge of interest [22-33]. Nonmetal-based benzylic
oxidations have also been mediated by species including, but
not limited to, electron deficient quinones, photoexcited organic
dyes and transition metal complexes, hypohalous acids, and
persulfate anions [12,34-40].
An important class of catalyzed benzylic C–H to C–O transfor-
mations are those catalyzed by N-oxyl radicals. Specifically,
N-oxyl radical catalysts based upon the N-hydroxyphthalimide
(NHPI) scaffold have been intensely studied for their ability to
mediate hydrogen atom abstraction using a terminal oxidant of
molecular oxygen [40-45]. NHPI has also been used in the
effective C–H to C–O functionalization of benzylic positions
using oxidants other than molecular oxygen including NO and
HNO3 [46-48]. In the work that follows, we report the selective
monooxygenation of secondary benzylic C–H bonds of simple
aryl alkanes using a combination of iodate and catalytic
N-hydroxyphthalimide (NHPI), which complements the selec-
tivity and capabilities of existing published work.
Results and Discussion
Figure 1: Catalyst optimization for the monooxidation of n-butylben-
We have recently reported a system of simple combinations of
an iodine (III, V, or VII) oxide with a catalytic amount of chlo-
ride for the direct oxygenation of methane to its methyl ester
[49,50]. Mechanistic studies of this system have indicated that
these chloride-iodate oxidations occur via a radical pathway
mediated in part by chlorine radicals [51]. While the chloride-
iodate system was effective in the functionalization of light
hydrocarbons and certain model compounds, it exhibited poor
functional group tolerance. Oxidation of complex hydrocarbons
led to a mixture of intractable products, which were in many
cases polyfunctionalized. Additionally, substrates containing
arene rings were shown to inhibit aliphatic C–H functionaliza-
tion via electrophilic trapping of reactive halogen species to
form aryl chlorides and iodides.
zene mediated by the iodate anion.
The nature of the H-atom abstraction catalyst was then varied in
an effort to increase the yield of compound 3a upon oxidation
of n-butylbenzene. The presence of moderate electron with-
drawing or donating substituents (chlorine, bromine, or methyl,
respectively) slightly lowered the yield when compared to the
parent NHPI-type catalyst (catalysts 2b,d). On the other hand,
the use of the strongly electron-withdrawing 3-nitro-N-hydroxy-
phthalimide (2e) yielded no reaction, returning only starting
material. The lack of iodine production upon reaction with 2e as
the catalyst suggests that the strongly electron withdrawing
nitro substituent made the catalyst difficult to oxidize under the
reaction conditions. While NHPI (2a) shows an E1/2 of 1.065 V
the corresponding E1/2 of 3-nitro-N-hydroxyphthalimide (2e) is
higher at 1.135 V versus Ag/AgNO3 [52]. N-Hydroxysuccin-
imide (2f) and N-hydroxynapthylimide (2g) were both able to
Utilizing NHPI as a less reactive hydrogen atom abstraction
catalyst than the chlorine radical allowed for the more selective
tertiary acetoxylation of adamantane [51]. Nitroxyl radicals
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catalyze the oxidation of n-butylbenzene, albeit in slightly bonds using either wet nitromethane or dry acetonitrile, respec-
lower yield than NHPI. N,N’-dihydroxypyromellitimide (cata- tively [54,55].
lyst 2h), which was used as a successful catalyst in the C–H
fluorination of benzylic hydrocarbons [53], was also able to cat- The substrate scope of the developed benzylic C–H monooxy-
alyze the reaction yielding compound 3a in 81% yield.
genation reaction was examined via the oxidation of substrates
containing benzylic C–H bonds as well as other functional
The NHPI-catalyzed oxidation of n-butylbenzene (1a) was groups. The optimized conditions developed for the acetoxyla-
shown to be compatible with a variety of iodine(V) and tion of 1a were used in the effective oxidation of other sub-
iodine(VII) oxidants. As shown in Table 1, the use of potas- strates containing secondary benzylic C–H bonds. As shown in
sium periodate as the terminal oxidant in the NHPI-catalyzed Figure 2, treatment of p-bromo or p-chloroethylbenzene with
C–H acetoxylation reaction yielded the ester product 3a in mod- the optimized conditions cleanly yielded monooxidized acetate
erate (42%) yield. This contrasts with orthoperiodic acid esters 3b and 3c in 70 and 72% yield, respectively. Bibenzyl
(H5IO6), which yielded only electrophilic arene iodination. The and 1-ethylnaphthalene were also oxidized in reasonable yield
use of alkali metal iodate salts such as lithium, sodium, and to acetate esters 3i and 3h. The oxidation of the biologically
potassium iodate as the terminal oxidant yielded 3a in moder- active ibuprofen methyl ester yielded the secondary acetate 3k
ate to good yield (36–84%). Reactions utilizing iodic acid in 78% yield. Finally, the oxidation of 5-ethyl-2-(4-
(HIO3) and calcium iodate were relatively low-yielding, similar propylphenyl)pyrimidine to acetate ester 3l in 76% yield indi-
to what was observed in the related chloride-catalyzed methane cates that the developed catalytic system is tolerant of nitrogen-
oxidation system [49]. The oxidant producing the highest yield containing heterocycles. This reaction shows remarkable selec-
of 3a, 86%, was ammonium iodate. Moreover, deviation from tivity for the alkyl chain appended to the pyrimidine ring as
the initial 1:1 ratio of oxidant to substrate was shown to signifi-
cantly reduce the yield of monooxygenated product 3a. A com-
bination of iodate anion and NHPI has previously been utilized
in the oxidation of C–H bonds. Minakata and co-workers
recently reported a combination of catalytic NHPI and iodic
acid mediated the hydroxylation or amidation of tertiary C–H
Table 1: Oxidant optimization for the NHPI-catalyzed monooxidation of
n-butylbenzene (1a).
Oxidant
Iodine oxidation
state
Yielda
KIO4
+7
+7
+5
+5
+5
+5
+5
+5
+5
+5
42%
Trace
36%
84%
83%
17%
43%
86%
73%
74%
H5IO6
LiIO3
NaIO3
KIO3
Ca(IO3)2
HIO3
NH4IO3
NH4IO3 (0.9 mmol)
NH4IO3 (1.1 mmol)
aYields were determined by gas chromatography relative to an internal
standard of dodecane. All reported yields are the average of 3 indi-
vidual reactions.
Figure 2: NHPI-catalyzed oxidation of secondary benzylic C–H bonds
mediated by iodine(V). a100 °C for 18 h; b60 °C for 18 h.
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Figure 3: NHPI-catalyzed oxidation of di-benzylic C–H bonds mediated by iodate.
opposed to the propyl group attached to the benzene ring. We overall yield was lower. It is proposed that the stabilizing pres-
propose that the methylene group adjacent to the pyrimidine ence of two benzene rings on the monooxidized products acti-
ring possesses lower bond strength C–H bonds than those adja- vates the remaining benzylic C–H bond in a way that encour-
cent to the benzene ring. This difference in bond strength is ages overoxidation.
illustrated when comparing the benzylic C–H bonds of toluene
to that of 2-methylpyridine (89.7 versus 87.2 kcal/mol, respec- The oxidation of 1-methylnaphthalene, (6a) as shown in
tively) [56]. Moreover, the electron withdrawing nature of the Figure 4, indicates that functionalization of substrates contain-
pyrimidine nitrogen atoms will affect the pKa of the adjacent ing primary benzylic C–H bonds was also possible using the
secondary benzylic C–H bonds. The hydrogen atom abstraction NHPI-iodate system. Such functionalization, however, appears
from this position would then be influenced by the pKa of the
C–H bond via a proton coupled electron transfer (PCET) type
mechanism.
Additionally, as shown in Figure 2, 1,2,3,4-tetrahydronaphtha-
lene was functionalized in poor yield (23%) to its acetate 3g if
exposed to reaction conditions at lower temperatures (60 °C)
than were used for other substrates. At 100 or 150 °C, only
aromatization was observed, suggesting that monooxygenated
products are able to react further. We propose that acetoxylated
tetrahydronaphthalene eliminates acetic acid to yield dihydro-
naphthalene, which can be further oxidized by two electrons to
yield the stable naphthalene ring. Minisci and co-workers also
reported aromatization upon oxidation of tetrahydronaphtha-
lene using an acetoxylation system similar to that reported in
this work [57]. While the methodology described in this work is
tolerant of molecular functionality with moderate oxidative
stability such as esters and nitrogen-containing heterocycles, it
shows incompatibility with functional groups such as alkenes,
phenols, phenyl ethers, and alcohols, which are readily
oxidized.
The dibenzylic C–H bonds of fluorene and xanthene were also
able to be functionalized. Xanthene (4a) was over-oxidized to
the ketone (xanthone, 5a) in 57% yield (Figure 3). Similarly,
fluorene was oxidized to a mixture of 9-fluorenyl acetate (5b,
Figure 4: NHPI-catalyzed oxidation of substrates containing primary
and tertiary benzylic C–H bonds. aReaction performed using NaIO3
(1 mmol) at 100 °C for 18 h. Product detected using GC–MS.
31%) and fluorenone (5c, 20%). The same mixture of acetate
and ketone is observed at a higher temperature (150 °C), but the
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to be more limited in scope and yield than that of secondary formed by the oxidation of NHPI by HNO3 abstracts a C–H
benzylic C–H bonds in that 4’-methylacetanilide (6c), and bond from a substrate yielding an organic radical. The organic
methyl 4-methylbenzoate (6d) were unable to be functionalized. radical is then trapped by iodine to yield the alkyl iodide which
It is postulated that the increased bond strength of primary is subsequently functionalized by acetic acid to yield the acetate
benzylic C–H bonds when compared to secondary benzylic product.
C–H bonds makes them less able to be functionalized in this
catalytic system [56]. A similar preference for the oxidation of To examine if the catalytic system proposed in this work is
secondary benzylic positions over primary benzylic positions proceeding via a similar mechanism we examined several
was recently reported by Noël and co-workers in the aerobic ox- aspects of the NHPI-iodate system. A substrate deuterium
idation of C–H bonds catalyzed by decatungstate [58]. Sub- kinetic isotope effect (KIE) study indicated that the benzylic
strates containing tertiary C–H bonds, such as 1-isopropyl-4- C–H bond is broken more rapidly than the C–D bond of the
methylbenzene (6b), were essentially unreactive under the de- deuterated substrate. Catalytic oxidation of a stoichiometric
veloped conditions, returning starting alkyl arene with only a mixture of proteo and perdeutero ethylbenzene (8a,b) afforded
trace of acetoxylated product 7b (see Supporting Information a deuterium KIE of 3.21 ± 0.08 (Figure 5). The magnitude of
File 1, Figure S11) [59]. Previous work on the oxidation of this value indicates a primary KIE, which is observed with other
tertiary benzylic C–H bonds indicates that in other catalytic reported deuterium KIE values of benzylic C–H scission via
systems, NHPI is able to mediate the abstraction of a hydrogen PINO radicals. Deuterium KIE values for hydrogen atom
atom from a tertiary benzylic position. The identity and selec- abstraction by the PINO radical vary based upon conditions
tivity of the product produced, however, is strongly influenced such as temperature and solvent [63-65]. Ishii and co-workers
by the reaction conditions. Works by Ishii and co-workers on have shown that catalytic oxidation of ethylbenzene in acetic
the aerobic oxidation of cumene in acetic acid using catalytic acid solvent via PINO radical catalysis yields a competitive
NHPI and cobalt(II), resulted in a mixture of 2-phenyl-2- deuterium KIE of 3.8, similar to the system described herein
propanol, acetophenone, and phenol [60,61]. This lack of selec- [60].
tivity in the product was related in part to the propensity of the
cumene hydroperoxide intermediate to decompose into phenol The existence of a primary KIE suggests the cleavage of the
and acetone under acidic conditions [62]. Use of a less acidic benzylic C–H bond and formation of a benzylic radical during
solvent and lower reaction temperature drastically increased the or prior to the rate determining step of the reaction. Such a
selectivity for 2-phenyl-2-propanol in the NHPI-catalyzed oxi- mechanism is in line with other C–H oxidations catalyzed by
dation of cumene [57]. The reason why tertiary benzylic C–H NHPI [41,53,66,67]. It is proposed that formed aliphatic radi-
bonds, which are weaker than secondary and primary benzylic cals are trapped by molecular iodine which is produced under
C–H bonds, are unreactive in the system described within this catalytic conditions via the reduction of iodate. While iodine is
work is not immediately clear, however, increased steric produced under experimental conditions via the reduction of
constraints at a tertiary carbon may play a role.
iodate, it is not entirely clear what the origin of all the electrons
for this process is given that the benzylic oxidation is only a net
The catalytic system proposed herein is related to work 2 electron process. Previous research shows that the rate of
published by Minisci et al. that details the use of a catalytic radical trapping by molecular iodine nears diffusion control,
system using HNO3, dioxygen, iodine and NHPI in the acetoxy- similar to that of diatomic oxygen [68-70]. This process of
lation of C–H bonds [47]. Given this similarity, we believe that radical trapping was probed through the pyrolysis of tert-butyl
the two systems are operating by similar mechanisms. In the 2-(naphthalen-1-yl)ethaneperoxoate (10), a benzylic radical pre-
Minisci system, a phthalimide N-oxyl (PINO) radical, which is cursor [71], in the presence of molecular iodine. Heating of this
Figure 5: Competitive deuterium KIE for the oxidation of ethyl benzene by the NHPI-iodate system.
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acyl perester at 100 °C for 1 hour in the presence of molecular dation of formed benzylic iodide intermediates occurs in the
iodine yielded acetate ester 7a in 69% yield and the benzylic production of benzylic acetate the production of ester product
iodide 11 in 29% yield (Supporting Information File 1, Figures without the need for oxidation indicates that oxidation may not
S3 and S4). When heated, the perester will decompose to form be necessary.
the relatively stable benzylic radical. Such a radical is then
trapped by molecular iodine to form the benzylic iodide, which As shown in Figure 7, a radical-based catalytic cycle is pro-
is subsequently solvolyzed to yield the acetate ester product posed for the NHPI-catalyzed oxidation of benzylic C–H bonds.
(Figure 6). This mechanism of radical capture by iodine is simi- NHPI is oxidized by one electron by iodate to form the well-
lar to what we recently proposed for the chloride-iodate medi- characterized PINO radical. The PINO radical, which forms an
ated oxidation of methane and in line with similar processes de- OH bond of 88 kcal/mol upon hydrogen abstraction (Figure 7)
scribed in the literature, including the catalytic system de- [63], will preferentially attack the weaker C–H bonds at the
scribed by Minisci [47,51,54,55,72,73]. Minakata and benzylic carbon, forming a relatively stable benzylic radical,
co-workers reported that a similar catalytic cycle using iodic rather than C–H bonds with stronger bond dissociation enthalpy
acid and NHPI oxidation of formed alkyl iodide intermediate to values. The formed benzylic radicals are then captured by I2,
an iodine(III) species was necessary for the conversion to a generated in situ by the reduction of iodate. The benzylic iodide
substituted product [54,55]. While we cannot rule out that oxi- formed upon trapping is expected to be reactive, readily
converting to the corresponding ester in carboxylic acid media.
Conclusion
A metal-free method for the selective monooxygenation of sec-
ondary benzylic C–H bonds using a combination of iodate and
NHPI was developed. The oxidation of n-butylbenzene with
stochiometric iodate and catalytic NHPI resulted in the clean
conversion of substrate to 1-phenylbutyl acetate (3a) in 86%
yield. The scope of this reaction appears to be tolerant of
various functional groups including halide groups, esters, and
nitrogen-containing heterocycles, yielding monoxidized acetate
products in moderate to good yields. While the reaction condi-
tions were effective in the oxidation of secondary benzylic C–H
bonds, the reaction was less effective in the oxidation of prima-
ry benzylic C–H bonds. Moreover, substrates with tertiary
benzylic C–H bonds were unreactive despite having a weaker
Figure 6: Pyrolysis of an acyl perester in the presence of molecular
iodine.
C–H bond strength. Preliminary mechanistic studies indicate
that the reaction occurs via H-atom abstraction mediated by the
Figure 7: Proposed mechanism for the selective monooxygenation of benzylic C–H bonds.
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Supporting Information File 1
All experimental procedures, analytical data, and copies of
1H NMR spectra of all studied compounds.
[https://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-15-55-S1.pdf]
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The authors acknowledge the financial support of North Central
College and the Edward Taylor Eli Lilly Graduate Fellowship at
Princeton University to NCB. We thank Professor John T.
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of this work. Additionally, a portion of this research performed
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