NHPI and palladium cocatalyzed aerobic oxidative acylation of arenes through a radical process

Article abstract of DOI:10.1039/c5cc08945j

The NHPI and palladium cocatalyzed radical oxidative acylation of arenes with aldehydes and alcohols as acyl equivalents via selective C-H functionalization has been described. Molecular oxygen, the most environmentally friendly oxidant, was used as the terminal oxidant in this catalytic cycle.

Full text of DOI:10.1039/c5cc08945j

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DOI: 10.1039/C5CC08945J
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NHPI and palladium cocatalyzed aerobic oxidative acylation of
arenes through a radical process
Yu‐Feng Liang,a Xiaoyang Wang,a Conghui Tang,a Tao Shen,a Jianzhong Liu,a and Ning Jiaoa,b*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The broad array of NHPI (N‐hydroxyphthalimide) catalyzed
aerobic oxidative reactions has been significantly improved.12
NHPI could be oxidized to PINO (phthalimido‐N‐oxyl) by O2,
and then PINO generated in situ could initiate the followed
A NHPI and palladium cocatalyzed radical oxidative acylation of
arenes with aldehydes and alcohols as acyl equivalents via
selective C‐H functionalization has been described. Molecular
oxygen, the most environmentally friendly oxidant, was used as
the terminal oxidant in this catalytic cycle.
radical
oxidative
reactions.
Inspired
by
these
transformations,11,12 we tried to use NHPI/O2 to initiate the
benzoyl radical formation from benzaldehyde or benzyl alcohol
for Pd‐catalyzed C‐H acylation to afford diverse aryl ketones (c,
Scheme 1).13
Over the past decades, transition metal‐catalyzed direct
oxidative C‐H functionalization with high atom‐efficiency as
one of the most efficient and straightforward strategies to
construct complex molecules from simple starting materials
has been significantly developed.1 Among these oxidative
processes, a number of oxidants such as TBHP, K2S2O8,
Cu(OAc)2, DDQ, PIDA etc. have been widely employed.
Molecular oxygen is natural, inexpensive and environmentally
friendly and is thus considered as the ideal oxidant.2 With the
growing demand for sustainable synthesis, the direct oxidation
by using molecular oxygen as oxidant is highly desirable.3
Aryl ketones are ubiquitous structural motifs of natural
products, pharmaceutical compounds, as well as functional
materials.4 Various directing group assisted Csp2‐H bond
acylations of arenes with aldehydes,5 alcohols6 or toluenes7 as
acyl surrogates for the synthesis of aryl ketones were
described.8 Despite the significance, stoichiometric of oxidants,
typically 1‐12 equivalent of TBHP (5‐6 M in decane),9 were
employed in the above elegant reports.5‐8 In 2009, Cheng and
coworkers reported a significant Pd‐catalyzed acylation of
Scheme 1. Molecular oxygen as terminal oxidant for Pd‐
catalyzed C‐H functionalization.
arenes using air as the terminal oxidant through
β‐H
elimination process to afford aryl ketones, although the
substrates were limited to 2‐arylpyridines and aryl aldehydes
(a, Scheme 1).10
Recently, the aerobic oxidative radical process was
employed in the Pd‐catalysis to oxidaize Pd(II) to Pd(III or IV)
intermediate for the subsequent reductive elimination
enabling the new chemical bond formation (b, Scheme 1).11
Our initial investigation began with the direct C‐H benzoylation
of acetophenone O‐methyl oxime (1a) under 1 atm of O2 with
benzaldehyde (2a) as the acylation reagent (see ESI). To our delight,
when the reaction was conducted using 10 mol % Pd(OAc)2 and 20
mol % NHPI as cocatalyst in CH3CN, the desired acylation product
(3aa) was obtained in 20% yield (Table S1, entry 1). Solvent
screening demonstrated that the choice of solvent is crucial for this
transformation. When THF, DMF, or PhCF3 was employed as the
solvent, the product was formed in only trace amount (entries 2‐4).
The reaction conducted in PhCl, DCE gave 3aa in 31% and 67% yield,
respectively (entries 5‐6). We were pleased to find that the yield
could be improved to 74% when 1,4‐dioxane was used as the
solvent (entry 7). No product was detected when NHPI was
a. State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School
of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191,
China, Fax: (+86)‐010‐8280‐5297, E‐mail: jiaoning@pku.edu.cn.
b. State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China.
Electronic Supplementary Information (ESI) available: Detailed experimental
procedures and spectroscopic data. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2015, 00, 1‐3 | 1
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replaced by other single electron oxidant such as TEMPO, Cu(OAc)2
or BQ (entries 8‐10). Subsequently, several palladium catalysts were
screened. PdCl2, PdTFA2, and Pd2dba3 showed lower catalytic
activities than Pd(OAc)2 (entries 11‐13). The reaction worked well
under 1 atm of air with a slightly lower yield (entry 14). In contrast,
the reaction did not proceed under Ar (entry 15). The yield
decreased slightly when the temperature was lowed to 60 oC (entry
16). Notably, in the absence of either Pd(OAc)2 or NHPI, the
reaction failed to give the product (entries 17‐18, Table S1, ESI).
A broad range of O‐methyl oximes were subjected to the optimal
reaction conditions (Scheme 2). The acylation could tolerate various
substitutes at the para‐position such as OMe, t‐Bu, n‐Bu, CF3, and
NO2, affording the desired products 3ba‐3fa in moderate to good
yields. The halogen substituents were well tolerated in products
3ga‐3ha, enabling additional functionalization at these positions.
Generally, the electron‐rich substrates provide superior yields to
electron‐deficient substrates. The acylation of meta‐bromine‐
substituted acetophenone O‐methyl oxime preferentially occurred
at the less sterically hindered ortho‐position, to afford the
corresponding product 3ia as the sole product. In addition, O‐
methyl oxime which derived from benzophenone was also
converted to the corresponding product 3ka in good yield. 4‐
chromanone and 1‐tetralone O‐methyl oxime, with a bicyclic
scafford, reacted smoothly to provide 3la and 3ma, respectively.
Additionally, when alkylphenone O‐methyl oximes were tested, the
acylation still proceeded well to provide the corresponding
products 3oa‐3pa. It should be mentioned that this transformation
exclusively generated the monoacylated products in all cases, and
no bisacylated products were detected by 1H NMR or GC‐MS
analysis.
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DOI: 10.1039/C5CC08945J
Scheme 3. Molecular oxygen oxidative acylation of acetophenone
O‐methyl oxime with various aldehydes.
The scope of Pd‐catalyzed molecular oxygen oxidative acylation
of acetophenone O‐methyl oxime with various aldehydes was also
investigated (Scheme 3). And the acylation showed good
compatibility of substituents on the benzene ring of benzaldehydes,
such as Me, OMe, t‐Bu, Cl, F or even strong electron‐withdrawing
CF3 and CN groups, affording the corresponding products 3ab‐3ao
in moderate to good yields. To our delight, this acylation is not
limited to aryl aldehydes. Aliphatic aldehydes were also reactive
and afforded the desired products 3ap‐3au in moderate yields.
O
Ph
O
O
N
O
N
Pd(OAc)2 (10 mol%)
NHPI (20 mol%)
1,4-dioxane, 80 oC, 24 h
R2
R2
H
O
R1
R1
O
2 (1 atm)
1
2a
3
Ph
O
Ph
O
O
Ph
O
O
Ph
O
O
N
N
N
N
H3CO
t-Bu
n-Bu
3aa, 74%
Ph
3ba, 80%
Ph
3ca, 79%
Ph
3da, 61%
Ph O
O
O
O
O
O
O
O
N
N
N
N
F3C
Ph
O2N
Br
Cl
3ea, 57%
3fa, 50%
3ga, 53%
3ha, 59%
O
O
N
Ph
O
O
Ph
O
O
Ph
O
O
N
N
O
N
Scheme 4. Molecular oxygen oxidative acylation of acetophenone
O‐methyl oxime with benzyl alcohols.
F
Br
3ia, 58%
3ja, 44%
3ka, 86%
Ph
3la, 90%
Ph
Encouraged by the above discoveries, we further investigated the
possibility of using benzyl alcohols as the acylation reagents since
benzyl alcohols can be readily oxidized into benzaldehydes by NHPI
and O2. As shown in Scheme 4, many substituted benzyl alcohols,
including those with Cl, Br, and OCH3, could be used as the source
of acylation with 1,4‐dioxane as the solvent to give products 5aa‐
5ad.
Ph
O
N
O
O
O
Ph
O
N
O
O
N
N
O
5
3ma, 60%
3na, 58%
3oa, 63%
3pa, 65%
Scheme 2. Molecular oxygen oxidative acylation of different O‐
methyl oximes with benzaldehyde.
2 | J. Name., 2015, 00, 1‐3
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regenerate PdII catalyst and NHPI cocatalyst for theVnieewxAtrtcicaletaOlnyltiniec
cycle.
DG
DG
O
O
O
Pd(OAc)2 (10 mol%)
NHPI (20 mol%)
1,4-dioxane, 80 oC, 24 h
H
Ph
H
DOI: 10.1039/C5CC08945J
O
2 (1 atm)
6
2a
7
Ph
N
N
O
N
N
O
O
O
Ph
Ph
Ph
N
7aa, 82%
7ba, 60%
7ca, 88%
7da, 55%
iPr
N
O
N
N
N
O
NH
O
Me2N
O
O
N
N
O
O
Ph
Ph
Ph
Ph
7ea, 91%
7fa, 27%
7ga, 11%
7ha, 0%
Scheme 5. Molecular oxygen oxidative acylation with various
directing groups.
This acylation reaction conditions were equally applicable to
pyridine‐directed substrates (Scheme 5). The reaction of
benzo[h]quinoline, 1‐phenylpyrazole, 2‐phenylpyridine and 2‐
phenoxypyridine were examined and products 7aa‐7da were
obtained in moderate to good yields. 9‐Isopropyl‐6‐phenyl‐9H‐
purine, which is widely used in medicinal chemistry,14 could also be
benzoylated to generate 7ea in excellent yield. Unfortunately, this
acylation was not efficient to azobenzene and acetanilide, affording
the corresponding products 7fa‐7ga inrelative low yields. Phenyl
dimethylcarbamate were found to be unreactive and did not afford
the corresponding product 7ha.
Scheme 6. Proposed mechanism for the transformation.
In conclusion, we have described an efficient and atom‐
economic Pd(OAc)2 and NHPI cocatalyzed ortho oxidative C‐H
bond acylation of arenes. Notably, the use of molecular oxygen
(1 atm) as the terminal oxidant make this reaction sustainable
and practical. The reaction exhibits a good tolerance for a
broad range of functional groups and a variety of aldehydes,
and alcohols are able to be employed as acylation equivalents
to afford aryl ketones regioselectively. This work may broaden
the research into the areas of aerobic oxidations via a SET
process. Studies to elucidate the detailed reaction mechanism
and further synthetic application of oxidative generation of
acyl radical with molecular oxygen are ongoing in our
The acylation product of oxime ether 3aa could be smoothly
converted to isoindoline 8, a useful motif in bioactive molecules and
nature products,15 through the treatment with ZrCl4/NaBH4 in THF
(eq. 1). Moreover, 3‐hydroxy‐3‐phenylindanone
9 could be
obtained through the removal of the directing group with
HCl/dioxane and the followed intramolecular aldolization with
NaOH/DMSO. No H/D exchange was observed in the reaction of 1a‐ laboratory.
d5 (eq. 2), and the intermolecular kH/kD of 1a was determined to be
3.8 (eq. 3), which indicated that the C‐H activation process should
be irreversible in this transformation.
Financial support from National Basic Research Program of
China (973 Program) (grant No. 2015CB856600) and National
Natural Science Foundation of China (Nos. 21325206,
21172006) and National Young Top‐notch Talent Support
Program are greatly appreciated. We thank Yujie Liang in this
On the basis of the previous reports5‐12 and our own observations,
a tentative mechanism for the palladium‐catalyzed oxidative
acylation with molecular oxygen is depicted in Scheme 6. The
reaction of benzaldehyde or benzyl alcohol, NHPI with molecular
oxygen could afford the benzoyl radical and PINO radical with H2O
as the byproduct (also see Scheme 1). The two active radicals could
oxidize PdII intermediate A to PdIV intermediate B.11 Subsequent
reductive elimination occurs to afford acylation product and
group for reproducing the results of 3ha and 3ad
.
Notes and references
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View Article Online
DOI: 10.1039/C5CC08945J
Molecular oxygen, the most environmentally friendly oxidant, was used as the terminal oxidant for palladium‐catalyzed radical
oxidative acylation of arenes.
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