Iron-catalyzed oxidative C-C(vinyl) σ-bond cleavage of allylarenes to aryl aldehydes at room temperature with ambient air

Article abstract of DOI:10.1039/c9cc01995b

A general and selective iron-catalyzed allylic C-C(vinyl) σ-bond cleavage of allylarenes without the assistance of heteroatoms to give aryl aldehydes is reported. The unstrained carbon-carbon single bond cleavage reaction uses ambient air as the sole oxidant, proceeds efficiently at room temperature, and allows for exceptional functional-group tolerance, which addresses the long-standing challenges of current C-C bond cleavage/functionalization. Notably, the method enables rapid late-stage oxidation of complex bioactive molecules and can be used to expedite syntheses of natural products (vanillin and glucovanillin) from readily available chemical feedstocks.

Full text of DOI:10.1039/c9cc01995b

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C9CC01995B
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Iron-catalyzed oxidative C–C(vinyl) -bond cleavage of allylarenes
to aryl aldehydes at room temperature with ambient air
Binbin Liu,†a Lu Cheng,†a Penghui Hu,a Fangning Xu,a Dan Li,b Wei-Jin Gua and Wei Han*ab
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A general and selective iron-catalyzed allylic C–C(vinyl) -bond C−H bonds and a -bond.4 Consequently, catalytic activation of
cleavage of allylarenes without the assistance of heteroatoms to allylic C−C single bonds in unfunctionalized olefins remains
give aryl aldehydes is reported. The unstrained carbon–carbon unexplored to date, with the exception of specific substrates
single bond cleavage reaction uses ambient air as the sole oxidant, bearing strained rings,5 chelation-assisted groups,6 or electron-
proceeds efficiently at room temperature, and allows for withdraw groups to polarize the allylic C−C bonds.7
exceptional functional-group tolerance, which addresses the long-
Aryl aldehydes are versatile building blocks in organic
standing challenges of current C–C bond synthesis for natural products, pharmaceuticals, pesticides,
cleavage/functionalization. Notably, the method enables rapid and dyes.8 Although aerobic oxidative C–C single bond
late-stage oxidation of complex bioactive molecules, and can be cleavage has been employed for the synthesis of acids,9
used to expedite syntheses of natural products (Vanillin and esters,10 amides,11 nitriles,12 and ketones,13 it remains a
Glucovanillin) from readily available chemical feedstocks.
challenging task to use this strategy for the synthesis of
aldehydes, probably due to their easy overoxidation to the
carboxylic acids.14 Recently, Bi15 and Li16 reported two elegant
examples of aerobic oxidative C(CO)–C() bond cleavage of
ketones to aldehydes at 110-120oC. Despite the major
advances achieved in aerobic oxidative C–C bond cleavage, the
cleavable bonds are required to be adjacent to ketones,9a-d,10a-
Catalytic unstrained carbon–carbon
bond
cleavage/functionalization in the absence of directing groups is
highly desirable, but remains challenging.1 The level difficulty
of this transformation increases drastically when regio- and
chemoselectivity issues are present. In addition, as a result of
the high dissociation energies of the breaking unstrained C−C
bonds, the current means to cleave such thermodynamically
stable bonds suffer from the need for drastic conditions and
elevated temperatures (often above 100°C) which limit their
scope and functional-group compatibility.1 Allylarene motif is
extensively present in biologically active compounds2 and the
corresponding allylic C−C bond cleavage/functionalization has
attracted increased interest. However, this transformation
suffers from at least two big challenges: The HOMO/LUMO
orbitals of the nonpolar allylic C−C -bonds mismatch with the
frontier orbitals of catalysts, leading to an increased difficulty
of allylic C−C bond activation3; regio- and chemoselectivity
issues originates from the presence of more reactive allylic
d,11a-c,12a,13a
carboxylic acids,11d-e aldehydes,11f,13b oximes,9e,12b
cyanides,10e,11g and alcohols9f-g (Scheme 1, a).
A
groundbreaking method reported by Jiao and co-workers used
an alkyl azide reagent as the promoter to achieve allylic C–C
cleavage of simple olefins to give cinnamyl aldehydes with
DDQ as the oxidant.3 While powerful, this non-catalytic metho
d used a hazardous alkyl azide reagent and 10 equiv of
trifluoroacetic acid, thus limiting its scope and functional group
a) Previous works: The aerobic oxidative cleavage of unstrained C-C bonds
requires the assistance of adjacent Heteroatoms.
RO
O
O
O
OH
N
CN
OH
H
b) This work: Iron-catalyzed aerobic oxidative cleavage of C-C single bonds
in unfunctionalized olefins at room temperature.
O
[Fe] (10 mol%)
air
(Het)Ar
RT
, EtOH,
[Si-H],
a. Jiangsu Collaborative Innovation Center of Biomedical Functional Materials,
Jiangsu Key Laboratory of Biofunctional Materials, Key Laboratory of Applied
Photochemistry, School of Chemistry and Materials Science, Nanjing Normal
University, Nanjing 210023, China; E-mail: whhanwei@gmail.com
b. Hunan Provincial Key Laboratory of Materials Protection for Electric Power and
Transportation, School of Chemistry and Biological Engineering, Changsha
University of Science and Technology, Changsha 410114, China
(Het)Ar
- iron catalysis
- no heteroatoms or directing groups required
- room temperature
- ambient air as the sole oxidant
- late-stage oxidation of complex molecules
- exceptionally functional-group tolerance [B(OH)2,
ArOH, glycosyl, OH, CHO, COOH, pyridyl, OAc,
COOR, CN, NO2, F, Cl, Br, I, cyclopropyl, OCH3]
† These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1. Transition metal-catalyzed aerobic oxidative cleavage of unstrained
C−C single bonds.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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tolerance. Compared with allylic C–C -bond, allylic C–C(vinyl) primary intramolecular isotope effect (kH/kD =3.5) was
View Article Online
is more thermodynamically stable,4 thus leading to direct observed, indicating that deprotonaDtiOoIn: 10.i1s039t/hCe9CCo0v1e99ra5Bll
cleavage and functionalization of this -bond being turnover-limiting step (for details, see the ESI). Acetaldehyde
unexplored.3
was also detected by GC analysis of a reaction mixture (for
Here, we report a novel iron-catalyzed aerobic oxidative details, see the ESI). Additionally, no product was formed
allylic C–C(vinyl) -bond cleavage of allylbenzenes without the when the reaction of 1a was performed under nitrogen
assistance of heteroatms or directing groups to produce aryl atmosphere, confirming that the incorporated oxygen atom
aldehydes in high yields and selectivities (Scheme 1, b).17 This originates from the oxygen atmosphere. It is well-known that
catalytic method features exceptional functional-group aryl aldehydes can be obtained via tandem allylbenzenes
tolerance and the late-stage oxidation of structurally complex isomerization-oxidation cleavage.22 However, subjecting trans-
molecules, which are unprecedented by other C–C bond anethole (1a’) to our reaction conditions failed to give the
functionalizations to date. Notably, this transformation is aldehyde product, excluding the possibility of tandem
accomplished with ambient air as the sole oxidant at room allylbenzene isomerization-oxidation.
temperature.
Guided by the theory mentioned above, a more systematic
evaluation of various parameters with exposure of 1a to an iron
species and a hydrosilane under ambient air and room temperature
was carried out (Figure 2). We were pleased to find that the aerobic
oxidative allylic C–C(vinyl) -bond cleavage of 1a proceeded
smoothly to afford aldehyde 2a exclusively in 88% yield under
ambient air and 25 °C in the presence of 10 mol % FeCl3 and 3 equiv
TMDSO (Tetramethyldisiloxane) in EtOH without adding additional
ligands. No desired product but untouched starting material 1a was
observed when the reaction was performed in the absence of the
iron catalyst or hydrosilane (Entries 1 and 2), verifying the essential
nature of these components in the catalytic process. Replacing
FeCl3 with FeCl2, Fe(NO3)3·9H2O, or Fe(acac)3 as the catalyst gave 2a
in lower yields, respectively (Entries 3–5). TMDSO appeared to be
the choice of hydrosilane after the common hydrosilanes had been
tested, e.g., (EtO)3SiH (70%), (EtO)2MeSiH (58%), and PhSiH3 (81%)
(Entries 6–8). We have also tested the effects of other solvents on
the reaction efficiency. The use of iPrOH as the solvent led to a
moderate yield of 2a, while DMF or DMSO resulted in poor results
(Entries 9-10).
Olefin by an in situ-formed Fe hydride can be converted to alkyl
radical species18 that can be intercepted by O2 to give the alkyl
peroxide radical.19 It is well known that alkyl peroxide radicals
undergoing O–O bonds homolysis can give carbonyl compounds
and/or alcohols.19 We questioned whether the alkyl peroxide
radical could form the dioxetane intermediate which readily
undergoes C–C bond cleavage to provide the carbonyl product20
when an adjacent C–H bond is prone to deprotonation. In this
context, allylarenes would be ideal candidates for use as substrates
because they not only possess reactive benzylic C–H bonds, but also
are bench-stable, readily accessible, and widely prevalent in
bioactive compounds.2
Details of our design principle are depicted in Figure 1.
Initially, allylbenzene would abstract a hydrogen radical from
Fe hydride, in situ generated from Fe(III) species and
hydrosilane, to give reduced Fe(II) species II and alkyl radical
III.19 Deuterium labelling and radical-trapping experiments
(with galvinoxyl) support the origin of the hydrogen and the
presence of III, respectively (for details, see the ESI). Recently,
Baran group reported that olefin could abstract a hydrogen
radical from iron(III) hydride in situ generated from Fe(III)
species and PhSiH3, to give alkyl radical.18 Submission of 4-
allylanisole (1a) to the Baran’s reaction conditions18c resulted
in 85% yield of 4-methoxybenzaldehyde (2a), further
supporting the hydrogen radical transfer process involved in
our transformation. Subsequently, II and III would be trapped
by O2 to provide the Fe(III)-superoxo IV21 and the alkyl peroxi
ed radical V intermediates, respectively. At this point, IV-
assisted V deprotonation would form the dioxetane VI which
decompose readily to afford the aryl aldehyde product along
with acetaldehyde,20 and the Fe(III)-hydroperoxide VII which
would then undergo reduction by hydrosilane to close cycle. A
With the optimized iron-catalyzed aerobic oxidative C–C bond
cleavage reaction in hand, we examined the substrate scope of
allylarenes.
A variety of allylarenes with different electronic
properties and substitution patterns provided the corresponding
oxidative C–C bond cleavage products 2 with excellent reactivity
(Figure 3). For instance, ortho-, meta-, para-methoxyl- substituted,
as well as sterically hindered allylarenes proceed successfully (2a-
2d). Notably, in the case of 2c, the highly strained cyclopropyl
moiety, which generally undergoes smooth ring opening with
transition-metal catalysis, remained intact in this new reaction.
Additionally, aryl fluorides (2e and 2m), aryl iodide (2e), aryl nitrile
(2f), nitroarene (2g), aryl chloride (2n), aryl bromides (2o-2q and
2w-2x), esters (2s-2t), and even aryl carboxylic acid (2r) are also
compatible. Particularly noteworthy is the tolerance of oxidation-
FeCl3
[Si-H]
EtOH
Ar'
[FeIII
I
]
H
FeCl3 (10 mol%)
[Si-H]
O
TMDSO (3.0 equiv.)
EtOH (2 mL), air, RT
3 h
MeO
MeO
Entry
O
1a
2a,
88%
(0.25 mmol)
Ar'
O2
[FeIII
]
OOH
VII
Deviation from standard conditions
Yield (%)
[FeII]
II
Ar'
CH3CHO
III
1
2
no [Fe]
no [Si-H]
0
0
3
4
5
6
7
8
9
10
FeCl2 instead of FeCl3
Fe(NO3)3 9H2O instead of FeCl3
Fe(acac)3 instead of FeCl3
(EtO)3SiH instead of TMDSO
(EtO)2MeSiH instead of TMDSO
PhSiH3 instead of TMDSO
iPrOH instead of EtOH
DMF or DMSO instead of EtOH
55
8
[FeIII]-OO
IV
Ar'
O2
VI
54
70
58
81
64
10-15
O
O
Ar'
O
O
V
H
Figure 1 Mechanistic rationale for the iron-catalyzed aerobic oxidative
cleavage of C−C single bonds in allylbenzenes.
Yields of the isolated products are given; TMDSO: 1,1,3,3-Tetramethyldisiloxane.
Figure 2 Conditional optimization.
2 | J. Name., 2012, 00, 1-3
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FeCl3 (10 mol%)
Table 1 Late-stage oxidation of complex small moleculesa
O
View Article Online
Ar
Ar
TMDSO (3.0 equiv.), EtOH
1
2
air
, RT
DOI: 10.1039/C9CC01995B
FeCl3 (10 mol%)
O
Ar
Ar
TMDSO (3.0 equiv.), EtOH
H3CO
3
O
O
4
O
O
air
, RT
H3CO
Entry
1
Allylarene
Product
OCH3
O
H3CO
OCH3
2d
, 24 h, 78%
O
O
O
O
O
2a
2b
2c
, 3 h, 88%
, 9 h, 91%
, 12 h, 78%
H
H
O
H
3a
OCH3
O
H
H
H3CO
H
OCH3
24 h 68%
F
O
O
H3CO
O
O
O
O
O
4a,
,
O
HO
O
OH
O
OH
OCH3
O
O
O
CN
O
NO2
HO
H
I
2
3
HO
H
H
O
H
2e
2f
2g
2h
, 9 h, 84%
, 24 h, 62%
, 24 h, 80%
,12 h, 62%
H
O
H
H
OH
H
H3CO
3b
H3CO
OH
4b
, 24 h, 78%
(HO)2B
O
OH
O
O
O
O
O
HO
2j
F
2m
3c
O
2i
2k
2l
, 9 h, 90%
, 24 h, 85%
, 24 h, 86%
, 12 h, 90%
, 12 h, 82%
O
O
H3CO
O
O
O
O
O
O
O
O
O
O
HO
H3CO
O
O
OCH3
Br
Br
O
Cl
4c, 24 h, 82%
Br
OCH3
H3CO
O
H3CO
O
2n
2o
2p
2q,
2r,
24 h, 65%
, 12 h, 87%
O
, 12 h, 86%
, 12 h, 82%
12 h, 87%
AcO
AcO
O
4
5
AcO
AcO
O
3d
4d
O
, 24 h, 82%
O
O
OAc
AcO
O
OAc
AcO
OHC
H3CO
O
O
O
N
H3CO
H3CO
OCH3
H3CO
O
H3CO
O
OCH3
24 h, 71%
HO
HO
HO
HO
4e
, 12 h, 86%
2s,
2t
2u
2v,
O
, 24 h, 60%
, 24 h, 66%
12 h, 87%
O
3e
Glucovanillin
O
OH
OH
HO
HO
O
O
O
O
S
a Yields of the isolated products are given.
2w
, 24 h, 68%
2x,
24 h, 68%
O
S
O
Br
O
O
OCH3
OCH3
Br
ing three oxidation-labile hydroxy groups, was proceeded well with
high selectivity. A Vitamin E succinate derivative 3c also afforded
the product 4c in 82% yield. Furthermore, biologically relevant
molecules 3d-3e having glycoside moieties were identified as viable
substrates. Remarkably, an unprotected carbohydrate fragment in
3e was compatible with the oxidative C–C bond cleavage reaction
and gave Glucovanillin (4e, 86% yield) that is present in the green
seed pods of Vanilla planifolia and is used extensively in
pharmaceutic aid.25 Generally, the late-stage functionalization of
medicinally relevant compounds with high chemoselectivity of the
iron-catalyzed oxidation is an unique advantage over the known
oxidative C–C bond cleavage reactions.
In summary, we have developed a general and selective iron-
catalyzed allylic C–C(vinyl) single bond cleavage of allylarenes
without the assistance of heteroatoms to give aryl aldehydes by
using 1 atm of air as the sole oxidant. High yield and selectivity are
achieved even at room temperature. The extremely mild conditions
enable exceptional functional-group tolerance, which is inaccessible
using current C–C bond-cleavage reactions. Notably, the unstrained
carbon–carbon cleavage/oxidation is particularly useful for late-
stage oxidation of structurally complex molecules, and allows
unprotected synthesis of Vanillin and Glucovanillin from readily
available chemical feedstocks. Considering the wide utility of aryl
aldehydes, these results will certainly pave the way for important
applications in both the academic and industrial fields through the
cost efficiency and shortening of synthetic sequences.
Figure 3 Substrate scope. Reported yields are for the isolated products.
labile phenols (2h-2j), aryl boronic acid (2k) and aryl aldehyde (2t),
and strong coordinating pyridyl group (2v), which is a formidable
challenge in C–H/C–C bond functionalization and highlights again
the excellent chemoselectivity of this method. Furthermore, the
reaction can move beyond the simple aryl group. For example, allyl-
substituted naphthalene, pyridine, thiophene, and furan are
competent substrates (2u-2x).
Apart from allylbenzenes, homoallylbenzene (1y) is also
amenable to the iron-catalyzed oxidative C–C bond cleavage by
increasing the reaction temperature to 80 °C and using CH3CN as
solvent [eqn (S2) in the ESI]. To our delight, unactivated internal
olefin 1z can be conveniently converted into the aldehyde 2l under
ambient reaction conditions [eqn (S3) in the ESI]. Although 1,2-
diarylethene 1aa doesn’t belong to the allylbenzene class, it is also
suitable for the reaction, still consistent with our design principle
[eqn (S4) in the ESI].
Vanillin is a natural product, which can be isolated from vanilla
beans and pods, pine woods, and roasted coffee,23 and a popular
flavoring material widely employed in foods, beverages, and
pharmaceuticals.24 Its manufacturing from eugenol (1h) requires
two steps (isomerization and oxidation) (Scheme S2 in the ESI) and
suffers from efficiency and selectivity issues.22 In our case, vanillin
(2h) was synthesized in 84% isolated yield with high selectivity in
one step under environmentally benign conditions (Figure 3, 2h).
Moreover, the reaction could be performed on a larger scale (5
mmol) without substantial erosion of the yield under 1 atm of O2
(Scheme S2 in the ESI).
To further demonstrate the practicality of the process, more
structurally intricate contexts were tested under the standard
reaction conditions (Table 1). For instance, 3a derived from
epiandrosterone, was readily oxidized to provide the desired
aldehyde 4a in 68% yield. Notably, a cholic acid derivative 3b bear-
The work was sponsored by the Natural Science Foundation of
China (21776139, 21302099), the Natural Science Foundation of
Jiangsu Province (BK20161553), the Natural Science Foundation of
Jiangsu Provincial Colleges and Universities (16KJB150019), and the
Qing Lan project.
Conflicts of interest
This journal is © The Royal Society of Chemistry 20xx
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(g) L. Xu, Y. Chen, Z. Shen, Y. Wang and M. Li, Tetrahedron
There are no conflicts to declare.
View Article Online
Lett., 2018, 59, 4349.
DOI: 10.1039/C9CC01995B
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DOI: 10.1039/C9CC01995B
Iron-catalyzed oxidative C–C(vinyl) -bond cleavage of allylarenes to
aryl aldehydes at room temperature with ambient air
Binbin Liu, Lu Cheng, Penghui Hu, Fangning Xu, Dan Li, Wei-Jin Gu and Wei Han*
– Table of Contents Entry –
H3CO
Fe
HO
HO
O
O
O
Ar
R
Ar
R
TMDSO, air (1 atm), RT
O
OH
Glucovanillin,
HO
86%
R: B(OH)2, (Ar)OH, glycosyl, OH, CHO, COOH, pyridyl,
OAc, COOR, CN, NO2, F, Cl, Br, I, cyclopropyl, OCH3
The iron-catalyzed C−C single bond cleavage and oxidation of allylarenes without
the assistance of heteroatoms/directing groups to produce aryl aldehydes is disclosed.