Visible-Light-Promoted Redox-Neutral Cyclopropanation Reactions of α-Substituted Vinylphosphonates and Other Michael Acceptors with Chloromethyl Silicate as Methylene Transfer Reagent

Article abstract of DOI:10.1002/adsc.201800761

The alkene cyclopropanation with chloromethyl silicate as a methylene transfer reagent has been accomplished via visible-light-mediated redox-neutral catalysis. This method features broad functional group tolerance and mild conditions. In addition to α-substituted vinylphosphonates, a range of Michael acceptors including α,β-unsaturated acrylate, ketone, amide and sulfone are suitable substrates for this photocatalytic cyclopropanation. An application of this protocol to the cyclopropanation of estrone derivative is also presented. (Figure presented.).

Full text of DOI:10.1002/adsc.201800761

Title: Visible-Light-Promoted Redox-Neutral Cyclopropanation
Reactions of α-Substituted Vinylphosphonates and Other Michael
Acceptors with Chloromethyl Silicate as Methylene Transfer
Reagent
Authors: Ting Guo, Li Zhang, Xiaobo Liu, Yewen Fang, Xiaoping Jin, Yi
Yang, Yan Li, Bin Chen, and Minghui Ouyang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201800761
Link to VoR: http://dx.doi.org/10.1002/adsc.201800761

10.1002/adsc.201800761
Advanced Synthesis & Catalysis
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Visible-Light-Promoted Redox-Neutral Cyclopropanation Reactions of
α-Substituted Vinylphosphonates and Other Michael Acceptors with
Chloromethyl Silicate as Methylene Transfer Reagent
Ting Guo,b Li Zhang,c Xiaobo Liu,a Yewen Fang,a,d,* Xiaoping Jin,c,* Yi Yang,a Yan
Li,b,* Bin Chen,a and Minghui Ouyanga
a
School of Materials and Chemical Engineering, Ningbo University of Technology, No. 201 Fenghua Road, Ningbo
315211, China E-mail: fang@nbut.edu.cn
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials and Ministry-of-Education Key
b
Laboratory for Synthesis and Application of Organic Functional Molecules, Hubei University, No. 368 Youyi Dadao,
Wuhan 430062, China E-mail: liyanok@hubu.edu.cn
Department of Pharmaceutical Engineering, Zhejiang Pharmaceutical College, No. 888 Yinxian Avenue East, Ningbo
c
315100, China E-mail: jinxp@mail.zjpc.net.cn
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
d
345 Lingling Road, Shanghai 200032, China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
and co-workers uncovered a new photocatalytic
Abstract: The alkene cyclopropanation with chloromethyl
silicate as
a
methylene transfer reagent has been cyclopropanation reaction of styrenes[10a] and Michael
acceptors[10b] employing diiodomethane as the
methylene source.
accomplished via visible-light-mediated redox-neutral
catalysis. This method features broad functional group
tolerance and mild conditions. In addition to α-substituted
vinylphosphonates, a range of Michael acceptors including
α,β-unsaturated acrylate, ketone, amide and sulfone are
suitable substrates for this photocatalytic cyclopropanation.
An application of this protocol to the cyclopropanation of
estrone derivative is also presented.
The
cyclopropylphosphonates
and
cyclopropylphosphonic acids are important cyclic
structural motif and found in many useful
biologically
active
natural
products
or
pharmacologically interesting compounds.[11] 1-
Arylcyclopropylphosphonates are conformationally
constrained analogs of 1-arylethylphosphonic acids
which are phosphorus analogs of 2-arylpropionic
acids (a well-known class of nonsteroidal
antiinflammatory and analgesic drugs such as
naproxen and ibuprofen). However, among the many
available methods for the preparation of
cyclopropylphosphonates,[12] the access to 1-
Keywords: Photoredox catalysis; Cyclopropanation;
Radical; Michael acceptor; 1-Arylcyclopropylphosphonate
The cyclopropane derivatives are important cyclic
structural motif and found in many useful
arylcyclopropylphosphonate
is
still
limited.
According to the Beletskaya method,[13] 1-
arylcyclopropylphosphonates could be accessed via
biologically
active
natural
products
or
pharmacologically interesting compounds.[1] They are
also useful synthetic intermediates due to their unique
structural and electronic characteristics.[2] Among the
two
steps
involving
treatment
of
1-
arylethenylphosphonic acids or their esters with
diazomethane followed by thermolysis of 3-aryl-4,5-
dihydro-3H-pyrazol-3-ylphosphonates. Intrigued with
our photoredox-catalyzed Giese-type reactions[14] of
α-aryl vinylphosphonates,[15] we envisioned that the
interesting 1-arylcyclopropylphosphonates would be
numerous
available
methods,[3]
alkene
cyclopropanation with a methylene transfer reagent
represents a conceptual and convenient methodology.
As for the preparation of cyclopropane ring with
unsubstituted carbon atoms, significant progress has
been achieved via CH2 group transfer reactions of
olefins employing (iodomethyl)zinc carbenoids,[4]
diazomethane,[5] and ylide[6] as the methylene
resource.[7] Among available synthetic approaches
toward accessing cyclopropanes from alkenes using
photocatalysis,[8] the parent CH2 transfer reaction of
alkenes by means of visible-light photoredox
catalysis was still rarely explored.[9] Recently, Suero
accessible
via
photocatalytic
cascade
ClCH2· addition/cyclopropanation reactions. Herein,
we report a general and efficient protocol for the
cyclopropanation of alkenes with chloromethyl
silicate[16,17] as the methylene source by means of
visible-light photoredox catalysis.
1
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10.1002/adsc.201800761
Advanced Synthesis & Catalysis
Table 1. Optimization of the reaction conditions.[a]
(a) [3+2] cycloaddition followed by thermolysis
reactions (Beletskaya et al.)
(b) cyclopropanation of alkenes via photocatalytic
CH2 transfer reaction (this work)
entry solvent photocatalyst
yield
(3a, %)[b]
[18-C-6] = 18-crown-6 ether
1
THF
Ir[dF(CF3)ppy]2(dtbbpy)PF6
42
43
49
59
91
87
trace
20
0
2
CH3CN Ir[dF(CF3)ppy]2(dtbbpy)PF6
Scheme 1. Synthetic approaches toward accessing 1-
arylcyclopropylphosphonates.
3
DMF
DMA
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Ir[dF(CF3)ppy]2(dtbbpy)PF6
4
5
DMSO Ir[dF(CF3)ppy]2(dtbbpy)PF6
DMSO 4CzIPN
To test the feasibility of this cyclopropanation
6
reaction,
we
initially
selected
α-phenyl
7
DMSO fac-Ir(ppy)3
vinyphosphonate 1a as the model substrate and
chloromethyl silicate 2 as the methylene source.
8
DMSO [Ru(bpy)3](PF6)2
DMSO no
Fortunately,
the
desired
1-phenyl
9
cyclopropylphosphonate 3a was isolated in 42% yield
when a solution of 1a with 2.0 equiv of 2 in the
presence of Ir[dF(CF3)ppy]2(dtbbpy)PF6 (2 mol %) in
THF (0.02 M) was illuminated with blue LEDs (9 W)
at room temperature for 12 h (entry 1). Among the
solvents tested, the optimal yield was observed
employing DMSO as the solvent (entries 2-5). In
light of the photocatalysts (entries 5-8), the organic
dye 1,2,3,5-tetrakis(carbazolyl)-4,6-dicyanobenzene
(4CzIPN)[18] gave a similar result under the examined
condition (entry 6). We also performed some control
experiments, which showed that the process was
completely inhibited in the absence of photocatalyst
(entry 9) or light (entry 10). Also the presence of
TEMPO resulted in no product formation (entry 11),
which suggests that radical plays a vital part in this
reaction.
10[c]
DMSO Ir[dF(CF3)ppy]2(dtbbpy)PF6
0
11[d] DMSO Ir[dF(CF3)ppy]2(dtbbpy)PF6
0
[a] Reaction conditions: a reaction mixture of 1a (0.2 mmol),
2 (0.4 mmol), photocatalyst (2 mol %), and solvent (6 mL)
was irradiated by 9 W blue LEDs at room temperature for
12 h.
[b] Yield of the isolated product 3a.
[c] The reaction was run in the dark.
[d] TEMPO (1 mmol) was added.
cyclopropylphosphonate 3k and Michael adduct was
obtained. Fortunately, the conjugate adduct could be
easily transformed into cyclopropylphosphonate via
intramolecular SN2 reaction with t-BuOK as the base
at room temperature[19] (see Supporting Information
(SI)). Also, appreciable formation of the Michael
adduct from an incomplete ring-closure event was
observed in the case of the aromatic rings bearing
strong electron-withdrawing groups (CO2Me, COMe,
CN, and NO2). Nicely, 48-88% isolated yields of
cyclopropylphosphonates 3l-o could be achieved after
12 h irradiation followed by treatment of t-BuOK.
With the optimized reaction condition in hand
(Table 1, entry 5), we assessed the scope with
vinylphosphonates,
and
the
desired
cyclopropylphosphonates were accessed in good to
high yields (Table 2). Generally, α-substituted
vinylphosphonates containing electron-donating
group such methyl or methoxyl on the phenyl ring
could be easily cyclopropanated to afford the
expected 1-aryl cyclopropylphosphonates 3b-g in
high yields. The presence of halogens was well
tolerated, providing opportunities for further
elaboration of the produced cyclopropanes. It is
worth noting that the electronics of the aromatic
moiety have a great impact on the outcome of the
cyclopropanation reactions. In the case of
cyclopropanation of the vinylphosphonate bearing
3,4-dichloro phenyl ring, a mixture of
Additionally,
alkenylphosphonates
possessing
naphthyl and biphenyl groups also worked
uneventfully to afford 3p and 3q in 86% and 96%
yields, respectively. Notably, heterocyclic furan-
containing vinylphosphonate also proved to be
competent for this transformation, albeit in somewhat
lower
cyclopropanation
corresponding n-butyl substituted
yield
(3r,
50%).
smoothly
Moreover,
afforded
the
the
2
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10.1002/adsc.201800761
Advanced Synthesis & Catalysis
Table 2. Scope of α-substituted vinylphosphonates.[a,b]
cyclopropanation of diethylvinylphosphonate was
fruitless and a complex mixture was obtained.
Encouraged by the results obtained with the
vinylphosphonates, we next turned our attention to
the cyclopropanation of different Michael acceptors 4.
With
α,β-unsaturated
acrylate
and
α,β-
unsaturatedketone as the radical acceptor, a mixture
comprising cyclopropane and radical adduct was
observed. After treatment of the mixture with t-
BuOK, the cyclopropane products 5a-d[20] were
isolated in 67-78% yields. Of note, no expected
product 5b was observed with triethylammonium
bis(catecholato)chloromethylsilicate as the methylene
transfer reagent.[21] Interestingly, α,β-unsaturated
amides could be cyclopropanated nicely to afford the
corresponding products 5e-f. Moreover, Morita-
Baylis-Hillman derived alcohol was also suitable
substrate for this photo-catalytic cyclopropanation
reaction, giving 5g in 73% yield. Moderate yield of
the cycopropane product 5h was obtained, plagued
notably by the formation of polymer/oligomer.[22]
With respect to the reaction of α,β-unsaturated
sulfone 6, a mixture consisting of phenyl 1-
phenylcyclopropyl sulfone 7 and radical adduct 8 was
obtained, affording 7 and 8 in 53% and 39% yields,
respectively. Indeed, direcet treatment of the reaction
mixture after irradiation with t-BuOK provided the
cyclopropane 7 in 88% overall yield of two steps.
Moreover, the cyclopropanation reaction took place
efficiently with treatmeant of t-BuOK of pure radical
adduct 8, producing 7 in 94% yield.
[a] Reaction conditions: a reaction mixture of 1 (0.2 mmol),
2 (0.4 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (2 mol %), and
DMSO (6 mL) was irradiated by 9 W blue LEDs at room
temperature for 12 h.
[b] Yield of the isolated product 3.
[c] Reaction time is 24 h.
[d]
Overall yield of two steps via 12 h irradiation followed
by treatment with t-BuOK in DMSO at room temperature
for 15-18 h (see SI).
cyclopropylphosphonate 3s in 63% yield. This result
clearly shows that the presence of an aromatic ring at
α-carbon of vinylphosphonate is not essential for the
successful cyclopropanation reaction. However, the
Table 3. Michael acceptor scope.[a,b]
Scheme 2. Photocatalytic cyclopropanation of vinylsulfone.
To demonstrate the application of this method in
pharmaceutical research, vinylphosphonate 9 derived
from estrone was selected as a representative
substrate
for
photocatalytic
redox-neutral
cyclopropanation reaction. Under standard catalytic
conditions, we are able to isolate the
cyclopropylphosphonate derivative 10 in 92% yield
(eq 1), which highlights the good functional group
tolerance and potential applicability of this visible-
light-promoted cyclopropanation reaction protocol in
complex settings.
[a] Reaction conditions: a reaction mixture of 4 (0.2 mmol),
2 (0.4 mmol), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (2 mol %), and
DMSO (6 mL) was irradiated by 9 W blue LEDs at room
temperature for 12 h.
[b] Yield of the isolated product 5.
[c] Overall yield of two steps via irradiation and treatment
of the mixture with t-BuOK (see SI).
3
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10.1002/adsc.201800761
Advanced Synthesis & Catalysis
with degassed DMSO (6 mL, 0.033 M). The tube was
irradiated with 9 W blue LEDs light strip spiraled
within a bowel for 12 h or 24 h. After complete
consumption of the starting alkene monitored by TLC,
the reaction was quenched by saturated Na2CO3
aqueous solution (10 mL), extracted with EtOAc (4 x
10 mL), and dried over MgSO4. After concentration
of the crude product in vacuo, flash chromatography
over silica gel afforded the product.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21202090), the Zhejiang Provincial
Natural Science Foundation of China (No. LY17B020004), the
Zhejiang Provincial Project of Applied Public Welfare
Technology (No. 2016C33254), the Ningbo Natural Science
Foundation (Nos. 2016A610234 and 2016A610237), and the
Scheme 3. Possible pathway for photocatalytic
cyclopropanation of alkenes.
On the basis of our study as well as literature
precedent, one plausible pathway through a redox-
neutral process is depicted in Scheme 3. The
National
Training
Programs
for
Innovation
and
Entrepreneurship for Undergraduates (No. 201611058006). The
authors acknowledge Professor Chaozhong Li (SIOC) for helpful
discussions.
photoexcited
*Ir[dF(CF3)ppy]2(dtbbpy)PF6
(E1/2
[*IrIII/IrII] = +1.21 V vs SCE in CH3CN)[23] acts as a
strong oxidant and undergoes a single electron
transfer (SET) with chloromethyl silicate 2 (Eox
=
+0.87 V vs SCE in DMF)[16] to generate ClCH2· 11.
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To an oven dried transparent 10 mL Schlenk tube
equipped
with
stirring
bar,
Ir[dF(CF3)ppy)]2(dtbbpy)PF6 (4.5 mg, 0.004 mmol,
0.02 equiv), potassium [18-Crown-6]
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5
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10.1002/adsc.201800761
Advanced Synthesis & Catalysis
COMMUNICATION
Visible-Light-Promoted
Redox-Neutral
Cyclopropanation Reactions of α-Substituted
Vinylphosphonates and Other Michael Acceptors
with Chloromethyl Silicate as Methylene Transfer
Reagent
Adv. Synth. Catal. Year, Volume, Page – Page
Ting Guo, Li Zhang, Xiaobo Liu, Yewen Fang,*
Xiaoping Jin,* Yi Yang, Yan Li,* Bin Chen, and
Minghui Ouyang
6
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