Photoinduced C—C Bond Cleavage and Oxidation of Cycloketoxime Esters

Article abstract of DOI:10.1002/cjoc.201800206

A novel structural reorganization of cycloketoxime esters beyond the traditional Beckmann rearrangement process has been established to build cyano-containing ketones in the presence of photocatalyst. This novel transformation is remarkable with selective C—C bond cleavage and an oxidation process enabled by DMSO used as the solvent, oxidant, and oxygen source avoiding acid, base and toxic cyanide salts as the cyano source. Further applications in late-stage modification of complex and chiral molecules have also been reported.

Full text of DOI:10.1002/cjoc.201800206

Photoinduced C-C Bond Cleavage and Oxidation of Cycloketoxime Esters†
Binlin Zhao,a Hui Tan,b Cheng Chen,a Ning Jiao,*,b and Zhuangzhi Shi *,a
ABSTRACT A novel structural reorganization of cycloketoxime esters beyond the traditional Beckmann rearrangement process has been established to
build cyano-containing ketones in the presence of photocatalysis. This novel transformation is remarkable with selective C-C bond cleavage and an
oxidation processes enabled by DMSO used as the solvent, oxidant, and oxygen source avoiding acid, base and toxic cyanide salts as the cyano source.
Further applications in late-stage modification of complex and chiral molecules have also been reported.
KEYWORDS C-C activation, radical, cycloketoxime, oxygenation, photocatalysis
Introduction
The cleavage and reorganization of C–C bonds is strategically
important to shift paradigm in retrosynthetic analysis.[1] It offers a
way of disconnecting inert bonds, providing a simultaneous
construction of two new chemical bonds from simple starting
materials. Strategies for C–C bond cleavage can be divided into
several mechanistic categories mainly including oxidative addition,
β-carbon elimination, migration and rearrangement. The most
ideal candidate to cleave a C–C bond utilizes small (three- and
four-membered) rings, in which the strain-release energy
associated with the cleavage event provides the major driving
force.[2] Catalytic activation of unstrained C–C bonds is much rarer
due to energetically less favourable C–C cleavage process.[3] In
2016, Dong et al. reported an important breakthrough for
rhodium-catalyzed activation of C–C bond in cyclopentanones, in
which an in-situ formed imine intermediate with a pendant
Figure 1 Development of a protocol for photoinduced C-C bond cleavage
directing group played the vital role for the success.[4] In this
and oxidation of cycloketoxime esters with DMSO.
context, the development of
a general process toward
functionalization of unstrained C–C bond with larger cyclic
ketones is highly desirable.
and other derivatives by C–C bond β-scission reactions of iminyl
radical[16] have been extensively exploited,[17] mild visible
light-driven variation[18] especially using unstrained rings has been
considerably overlooked.[19] Very recently, Leonori and coworkers
have developed oxidative generation of iminyl radicals from
less-strained cycloketoximes by organophotoredox, where the
short-lived nucleophilic carbon radicals could be captured by the
electrophilic reagents for fluorination, chlorination, and azidation
(Figure 2, left).[20] Inspired by recent Kornblum-type oxidation,[13,
Traditionally, the C–C bond cleavage of ketones involve
Baeyer-Villiger oxidation in combination with a strong oxidants.[5]
Another efficient strategy relies on the prefunctionalized ketones
with the release of functional fragments such as the classical
Beckmann rearrangement (Figure 1a).[6] The recent developments
entail cheap and cleavage and oxidation of cycloketoxime esters
with DMSO selective catalysis, high atom efficiency, and
environmentally friendly oxidants.[7] For example, Bi and Liu et al.
disclosed a Cu-catalyzed chemoselective cleavage of methyl
ketones to generate aldehydes under aerobic oxidative
conditions.[8] Jiao group also uncovered the conversion of ketones
to amides and esters through aerobic oxidative C-C bond cleavage
via copper catalysis.[9] In extention, herein, we report a novel
transformation of photocatalytic C−C bond cleavage of
cycloketoxime esters to construct cyano-containing ketones,[10] in
which DMSO acts as the terminal oxidant for oxygenation and the
oxime ester group is the source of nitrogen (Figure 1b). As an
inexpensive and low-toxic solvent, DMSO has been widely used as
the oxidant in several name reactions.[11] Recently, C–H oxidation
of benzenethiol,[12] diarylmethanes, toluenes,[13] ketones,[14] and
styrenes[15] using DMSO as the oxygen source have been reported
(Figure 1c). As a result, the development of a DMSO-mediated
oxidation event triggered by C-C bond cleavage will expand the
toolbox of reactions available to synthetic chemists.
15]
we hypothesized that a carbocation intermediate at benzylic
position should be formed after C-C bond cleavage which takes
part in a subsequent oxidation, thus necessitates the oxime to
undergo reductive visible-light-mediated single electron transfer
(Figure 2, right).
Results and Discussion
We began our studies by irradiating
a solution of
2-phenylcyclopentan-1-one-O-(4-(trifluoromethyl)benzoyl) (1aa)
with commonly used photocatalyst fac-Ir(ppy)3 using 5W blue
light emitting diodes (LEDs). By measuring the reduction potential
0/−1
of 1aa (Ep
= -1.00 V vs SCE in DMF), it shows that 1aa readily
undergoes one electron reduced by fac-Ir(ppy)3 {E1/2 [IrIV/IrIII*])
= -1.73 V vs SCE}.[21] To our delight, the reaction was indeed found
to be facile with 1.0 equivalent of 1aa in the presence of
fac-[Ir(ppy)3] catalyst (1.0 mol%) in DMSO, at room temperature
red
While catalytic thermal ring opening of cyclobutanone oximes
affording
the
desired
rearrangement
product
5-oxo-5-phenylpentanenitrile (2aa) in 86% yield (entry 1).
a State Key Laboratory of Coordination Chemistry, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing 210093, China.
E-mail: shiz@nju.edu.cn
Pharmaceutical Sciences, Peking University, Xue Yuan Road 38, Beijing 100191,
China.
E-mail: jiaoning@pku.edu.cn
b State Key Laboratory of Natural and Biomimetic Drugs, School of
†Dedicated to Professor Xiyan Lu on the occasion of his 90th birthday.
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been through the copyediting, typesetting, pagination and proofreading process, which
may lead to differences between this version and the Version of Record. Please cite this
article as doi: 10.1002/cjoc.201800206
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Table 2 Scope of the Ketoxime Esters.a
Figure 2 Proposed reaction pathway.
Control experiments run in the absence of photocatalyst (entry 2),
light (entry 3) or DMSO (entry 4) provided essentially no product.
Other ester substituents in substrates were also examined. The
0/−1
substrate 1ba displayed Ep
= -0.91 V vs SCE and afforded the
0/−1
product 2aa in similar yield (entry 5). In contrast, 1ca (Ep
=
-2.56 V vs SCE) having higher reduction potentials was not
suitable for the reaction (entry 6) and 1da (Ep 0/−1 = -1.72 V vs SCE)
suffer from poor conversion (entry 7). Although the reduction
profile of oxime 1ea (Ep 0/−1 = -0.88 V vs SCE) was matched with
the photocatalyst, however we detected the desired product 2aa
in 40% yield along with (E)-5-phenylpent-4-enenitrile as
a
byproduct (entry 8). Other screened photocatalysts, such as the
organic photocatalyst Eosin Y{(E1/2red [EY•+/EY*]) = -1.11 V vs SCE}
was found to be much less effective in this reaction (entry 9) and
red
Ru(bpy)3(PF6)2 {(E1/2 [RuIII/RuII*]) = -0.81 V vs SCE} could not
promote this process (entry 10).
With the set of optimized reaction conditions in hand, we first
examined the scope of various cycloketoxime O-(4-
(trifluoromethyl)benzoyl) in this C-C bond oxidation event (Table
2). A range of arenes with electron-neutral (1ab-1ad),electron-rich
Table 1 Reaction Development. a
Yield of
2aa (%) b
Entry
Variation from the “standard conditions”
1
2
none
86 (85) c
without fac-Ir(ppy)3
0
0
3
without light
4
DMF instead of DMSO
0
5
R = 4-CNPhCO (1ba, Ep 0/−1 = -0.91 V vs SCE)
R = PhCO (1ca, Ep 0/−1 = -2.56V vs SCE)
R = 4-NO2PhCO (1da, Ep 0/−1 = -1.72 V vs SCE)
Ar = C6F5CO (1ea, Ep 0/−1 = -0.88 V vs SCE)
Eosin Y instead of fac-Ir(ppy)3
Ru(bpy)3(PF6)2 instead of fac-Ir(ppy)3
81
0
6
a
Standard conditions: 1.0 mol% fac-Ir(ppy)3, 1 (0.20 mmol) in 2 mL DMSO
7
12
40
trace
0
b
with blue LEDs (5 W) at room temperature for 24 h, under argon.
8
Isolated yields. c 48 h.
9
(1ae-1af) and electron-deficient (1ag-1ah) substituents on
α-position of cyclopentanone derivatives were tolerated and
afforded the products in moderate to good yields. Notably,
2-naphthyl-derived 1al and thianaphthenyl-derived 1aj were also
suitable for this process to produce 2al-2aj in good yields.
Four-membered ring compound 1ak provided the desired product
10
a
Standard conditions: 1.0 mol% fac-Ir(ppy)3, 1aa (0.20 mmol, 1.0 equiv)
in 2 mL DMSO at room temperature for 24 h, under argon. b Determined
by GC. c Isolated yields.
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2ak in moderate yield. Remarkably, the method could achieve the
structural reorganization of other less-strained substrates
including the oxime esters derived from cyclohexanones (1al-1ao),
cycloheptanones (1ap-1aq) and even cyclooctanone (1ar), thus
converted into chiral cyano-containing ketones 9a-b with excellent
preservation of the enantiopurity (Scheme 1b). Very recently, Lu
and coworkers have also reported enantioselective intramolecular
α-arylation of cyclobutanones combining palladium and enamine
obtaining a broad range of ring-opening products 2al-2ao in 47-75% catalytic systems.[24] Further transformations of the synthesized
yields. Finally, the substrate scope of this mild rearrangement
protocol was also demonstrated by the C-C oxidation of the
acyclic compound 1as, forming the ketone 2as in 77% yield.
chiral cyclobutanones 11a-b had also shown the versatility our
method. As shown in Figure 1c, the desired chiral 4-chromanones
13a-b could be generated in good yields retaining the
enantioselectivity.
A major benefit of our mild, visible-light-induced C-C bond
cleavage procedure is its amenability in late-stage modifications.
To demonstrate this potential, ketone 3a-b derived from Estrone
was smoothly transformed to oxime esters 4a-b. These
compounds were in turn converted into the products 5a-b in
moderate to good yields, in which the C-C bond cleavage occurred
exclusively at the side adjacent to the aryl group (Scheme 1a).
Enantioselective α-arylation of ketone represents one of the most
important approaches for synthesis of optically active α-aryl
carbonyl compounds.[22] Our protocol receives an opportunity to
use these products by ring opening and oxidation. For instance,
according to Aggarwal’s method for α-arylation of cyclohexanones
with diaryl iodonium salts,[23] we could prepare chiral ketones
7a-b in good yields and high enantioselectivities. Ketoxime
esterfication furnished the compounds 8a-b, which were easily
To confirm the scalability of the present method, a scaled-up
reaction of 1aa was carried out, and product 2aa was readily
isolated in 77% yield. Subsequently, synthetic transformations of
the product were also conducted (Scheme 2). The cyano group
could be effectively transformed into the carboxylic acid 14 in
nearlyfull conversion with aqueous KOH. Meanwhile, the terminal
amide product 15 was synthesized in 87% yield using H2O2 as an
oxidant. Moreover, the radical cyclization occurred in the
presence of SmI2 to afford annulation product 16 smoothly.
Finally, the traditional Baeyer-Villiger oxidation of 2aa with
m-CPBA pro ceeded to give the ester 17 in 58% yield.
Scheme 1 Late-stage modification of complex and chiral molecules. (i) NH2OH∙HCl (1.5 equiv), aq. NaOH (2.0 equiv), then 4-CF3PhCOOH (1.5 equiv), EDCI
(2.5 equiv), DMAP (20 mol%); (ii) 1.0 mol% fac-Ir(ppy)3, oximes 4/8/12 (1.0 equiv) in DMSO with blue LEDs (5 W) at room temperature for 24 h, under
argon.
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2018xxxxx.
Acknowledgement
We thank the “1000-Youth Talents Plan”, the National Natural
Science Foundation of China (Grant 21772002, 21632001 and
2167020084) for financial support. We are also grateful to Prof.
Ping Lu at Fudan University for kindly providing some chiral
compounds.
Scheme 2 Functional group Transformations.
To further clarify the oxygen resource of the product and
verify our proposal, we operated the reaction in 18O-labeled
DMSO (89% of 18O) under the standard conditions. As anticipated,
the 18O incorporated product 2aa(18O) was obtained in high ratio
confirming that the oxygen atom in the product was derived from
DMSO itself (Scheme 3a). It’s also worth to mention that we
detected foul smell of dimethyl sulfide (DMS) when opening the
Schlenk tube. The addition of H218O to our reaction system could
not form any 18O incorporated product, which excludes the
possibility of H2O as the oxygen resource (Scheme 3b). In addition,
high yield of 2aa could be generated when the reaction was
carried out in the degassed DMSO (Scheme 3c). We therefore
believe that the oxygen resource is more likely to come from
DMSO instead of the water or oxygen in the air in line with our
proposed mechanism.
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Revised manuscript received: XXXX, 2017
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Entry for the Table of Contents
Page No.
Photoinduced C-C Bond Cleavage and
Oxidation of Cycloketoxime Esters
A SET-induced strategy has been established for C-C bond cleavage and oxidation
sequence of cycloketoxime esters in the presence of photocatalysis. The protocol is
distinguished by mild and safe reaction conditions that avoid peroxide, acid, base and
toxic cyanide salts.
Binlin Zhao,a Hui Tan,b Cheng Chen,a Ning
Jiao,*,b and Zhuangzhi Shi*,a
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