Rhodium(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Cyclization with Sulfoxonium Ylides to Naphthols

Article abstract of DOI:10.1002/adsc.201800362

Rhodium(III)-Catalyzed C?H activation of benzoylacetonitriles in coupling with sulfoxonium ylides was developed to synthesize diversified substituted naphthols, in which aryl, heterocyclic and alkyl groups in sulfoxonium ylides are tolerated. Intriguingly, we have further implemented transformation for 1-naphthols to give some intriguing fused tricyclic compounds and derivatives of propranolol, which demonstrate the practical utility of this methodology. (Figure presented.).

Full text of DOI:10.1002/adsc.201800362

Title: Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and
Cyclization with Sulfoxonium Ylides to Naphthols
Authors: chaofan zhou, feifei fang, Yilang Cheng, Yazhou Li, Hong Liu,
and Yu Zhou
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10.1002/adsc.201800362
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Rhodium(III)-Catalyzed C-H Activation of Benzoylacetonitriles
and Cyclization with Sulfoxonium Ylides to Naphthols
Chaofan Zhou a,b, Feifei Fangb, Yilang Chengb, Yazhou Lib, Hong Liub,* and Yu
Zhoub,*
a
Nano Science and Technology Institute, University of Science and Technology of China, 166 Ren Ai Road, Suzhou
215123 China.
b
Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, 555 Zu
Chong Zhi Road, Shanghai 201203, China. E-mail: hliu@simm.ac.cn; zhouyu@simm.ac.cn
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))
Abstract. Rhodium(III)-Catalyzed C-H activation of some intriguing fused tricyclic compounds and derivatives
benzoylacetonitriles in coupling with sulfoxonium ylides of propranolol, which demonstrate the practical utility of
was developed to synthesize diversified substituted this methodology.
naphthols, in which aryl, heterocyclic and alkyl group in
sulfoxonium ylides are tolerated. Intriguingly, we have
further implemented transformation for 1-naphthols to give
Keywords: C-H activation; Rhodium(III)-Catalyzed;
Benzoylacetonitriles; Sulfoxonium ylides; Naphthol
Introduction
Naphthols are an important class of structural motifs
in natural products and pharmaceuticals,[1] and have
received a great deal of attention recently because of
their unusual structures and interesting biological
properties, such as anti-HIV (mollugin),[2]
antiarrhythmic
(propranolol),[3]
antimalarial
(dioncophylline A and korupensamine A)[4] and
antitumor activities (gossypol)[5] (Figure 1).
Consequently, general methods for the synthesis of
such structural motifs have long been regarded as an
important target in synthetic organic chemistry.[6]
Although some well-established methodologies have
been reported, it is attractive to employ the C-H
activation strategy for straightforward access to these
naphthol derivatives.
Scheme 1. Rh (III) Catalyzed Synthesis of Naphthols.
In the past decades, Rh(III)-catalysts played
increasingly important roles in the activation of C-H
bonds to build heterocyclic scaffolds.[7] Wang and co-
workers reported a pioneering Rh(III)-catalyzed
oxidative
annulation
of
ortho-substituted
benzoylacetonitriles with diphenylacetylenes to
synthesize 3,4-diphenyl-1-naphthols, but these
naphthols could be obtained only when ortho-
substituted benzoylacetonitriles were used (Scheme
1a)[8], other benzoylacetonitriles underwent a cascade
annulation to give naphtho[1,8-bc]pyrans. These
results indicated that alkynes seem to be an effective
synthon to build 1-naphthols. Recently, Zhu’s group
Figure 1. Representative bioactive compounds with
naphthol skeletons.
1
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10.1002/adsc.201800362
Advanced Synthesis & Catalysis
and Li’s group reported two synthetic strategies to
prepare 3,4-diaryl-substituted naphthalenes and 3,4-
diaryl-substituted naphthols via rhodium-catalyzed C-
H activation of enaminones and phenylglyoxal-
detrimental to the yield of this transformation (entries
17 and 18).
With the optimal reaction conditions in hand, we
then sought to evaluate the scope and generality of
benzoylacetonitriles in the coupling with sulfoxonium
ylide 2a in this catalytic system. Diversified
derived
nitrones
with
alkyne
synthons,
respectively.[9,10] However, alkyl-alkyl alkynes were
not tolerated as the substrates in this transformation
and failed to give desired products. Besides, Li’s
group reported the other two synthetic strategies to
build more diversified naphthol derivatives by
employing phenacyl triphenylphosphonium salts and
nitrones as the starting materials via a Rh (III)-
catalyzed C-H activation and annulation (Scheme 1b
and 1c), respectively.[11,12] But these reaction systems
are limited to the employment of unavailable starting
materials.[13] Recently, sulfoxonium ylides were
widely used as excellent synthetic materials.[14] On
the basis of these challenges and our efforts in the
construction of heterocyclic scaffolds via Rh/Ru-
catalyzed transformations,[15] we herein report a novel
Rh(III)-catalyzed cascade transformation with
Table 1. Optimization of Reaction Conditionsa).
Additive
(x equiv)
yield (%)
entry
solvent
time (h)
3aa
1
2
MeOH
H2O
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOAc (2)
CsOPiv(2)
NaOAc(2)
AgOAc (2)
PivOH(2)
CsF(2)
12
12
12
12
12
12
6
30 b)
N.R.
14
3
THF
benzoylacetonitriles
and
sulfoxonium
ylides
4
PhMe
CH3CN
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
23
compounds to prepare diversified 3-substituted
naphthols, in which aryl, heterocyclic and alkyl group
in sulfoxonium ylides are tolerated. More importantly,
the intriguing naphthols could be converted into the
derivatives of propranolol which is an antiarrhythmia
drug in clinic (Scheme 1d). It is worth mentioning
that during our submission Li’s group also reported a
very similar strategy to build the intriguing naphthol
and naphtho[1,8-bc]pyran derivatives.[16]
5
27
6
46
7
81
8
3
57
9
6
75
10
11
12
13
14
15
16
17
6
N.R.
N.R.
N.R.
45
Results and Discussion
6
6
We initiated our studies by exploring the coupling of
benzoylacetonitrile 1a (0.1 mmol) with sulfoxonium
ylide 2a (0.12 mmol) in the presence of [Cp*RhCl2]2
(4.0 mol %) as the catalyst and CsOAc (2 equiv) as
6
Cs2SO4(2)
CsOAc(1)
-
6
30
o
the additive in MeOH at 80 C for 12 h, and the
6
65
desired product 3aa was achieved at 30% yield
(Table 1, entry 1). Its structure was unambiguously
6
N.R.
12 c)
23 b)
1
confirmed by its H and 13C NMR spectra, mass
CsOAc (2)
CsOAc (2)
6
spectrometry data, and X-ray crystallographic
analysis,[17] respectively. Based on this result, we
have further explored the reaction conditions.
18
6
a)
o
Reaction condition: 1a (0.1 mmol), 2a (0.12 mmol),
Through the change of solvent at 50 C, the yields of
[Cp*RhCl2]2(4.0 mol %), additive (x equiv) in the solvent
3aa occurred disappointing decrease in most solvents,
and DCE gave the best yield (entries 2-6). We noted
that the starting materials disappeared completely and
many impurities were observed using DCE as the
solvent for 12 h. Therefore, we attempted to shorten
the reaction time and the results displayed that a
better yield (81%) was delivered for 6 h (entries 7-8).
Further screening of the additives showed CsOAc
proved to be the best choice for this transformation
(entries 9-14). Reducing the additive loading to 1
equiv resulted in a lower yield, only 65% of desired
product was obtained (entry 15). Further investigation
showed that the target product could not be found in
the absence of CsOAc (entry 16). Additionally,
raising or lowering the reaction temperature was
o
(3 mL) at 50 C for time (h). THF = tetrahydrofuran. DCE
= 1,2-dichloroethane. N.R. = no reaction. b) 80 oC. c) Room
temperature.
benzoylacetonitriles bearing various aryl moieties
substituted by electron-donating groups, electron-
withdrawing groups and halide groups were explored
and the results demonstrated that a smooth coupling
with sulfoxonium ylide 2a could be detected and the
desired products were obtained with moderate to
good yields (Table 2, 3aa-3oa, 63-87%). Among
them, the benzoylacetonitrile substrates with the para
position substituted by various electron-withdrawing
groups and halides, such as -CF3, -F, -Cl and -Br
2
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10.1002/adsc.201800362
Advanced Synthesis & Catalysis
could be smoothly converted into the desired
products with 63%-77% yields (Table 2, 3ba-3ea).
Introduction of the electron-donating groups
(methoxyl, methyl and tert-butyl) to the para position
of benzene ring of benzoylacetonitrile 1a was also
tolerated to the standard reaction conditions, and the
reaction yields were maintained at a higher level
(Table 2, 3fa-3ha). We further introduced -F, -OCH3
and -CH3 groups into the 3-position of benzene ring
of benzoylacetonitrile 1a and good results were also
obtained (3ia-3la, 72−77%). However, introduction
Some synthetic utilities of this protocol were
explored. As shown in Scheme 2, a gram-scale
preparation of product 3aa was carried out with 71%
isolated yield. Oxidative coupling of the naphthol
product 4ad with diphenylacetylene delivered the
fused tricyclic compound 6 with 55% yield, and its
analogues were widely used in solid-state
fluorescence (Scheme 2b).[18] More intriguingly, the
naphthol 4aj could readily be converted to the
derivative of propranolol 8, which is a sympatholytic
nonselective beta blocker and used to treat anti-
arrhythmia,[19] with a simple two-step operations
(Scheme 2c).
Table 2. Substrate Scope of Benzoylacetonitrilesa)
With the established substrate scope and utility of
the product, we conducted a series of studies to
elucidate the possible mechanism. Several H/D
exchange experiments were carried out (Scheme 3).
The C-H bond cleavage was likely involved in the
turnover-limiting step, as evidenced by the rather
large values of kH/kD = 2.3 (measured from the
competition experiment) and kH/kD = 3.4 (measured
from parallel reactions) as shown in Scheme 3a. To
determine the reversibility of the C-H activation step,
a hydrogen-deuterium exchange experiment of 1a
was carried out using D2O under standard conditions.
Both the methylene proton and ortho C-H were
deuterated by 20% (Scheme 3b), indicating the
reversibility of the C(methylene)-H and the C(aryl)-H
bond cleavage.
Table 3. Substrate Scope of Sulfoxonium ylide Compoudsa)
a)
Reaction condition: 1 (0.1 mmol), 2a (0.12 mmol),
[Cp*RhCl2]2 (4.0 mol %), additive (2 equiv) in DCE (3 mL)
o
1
at 50 C for 6 h. b) Determined by H NMR analysis of the
crude reaction mixtures.
of -OCH3 group brought a geometric isomer, a small
amount
of
1-hydroxy-5-methoxy-3-phenyl-2-
naphthonitrile was detected (Table 2, 3ka). In
addition, the naphthalene ring and thiophene ring
derivatives were also well tolerated in this reaction
(Table 2, 3ma, 3na, 3oa).
The scope of sulfoxonium ylides was further
examined (Table 3). Sulfoxonium ylides bearing
various electron-donating and electron-withdrawing
substituents such as methyl, methoxy, halogen, and
trifluoromethyl groups at the 4-position (or 3-position)
of benzene ring all could couple smoothly with 1a in
excellent yields (Table 3, 4aa−4ag). Introduction of
naphthalene or thiophene ring was also tolerated and
gave good results (Table 3, 4ah-4ai). More
importantly, replacing R2 group with different
alkyl and cycloalkyl groups could also react
smoothly with 1a to provide the 3-alkyl
substituted 2-cyanonaphthols (Table 3, 4aj-4an)
with moderate to high yields (55%-74%).
a)
Reaction condition: 1a (0.1 mmol), 2 (0.12 mmol),
[Cp*RhCl2]2 (4.0 mol %), additive (2 equiv) in DCE (3 mL)
at 50 oC for 6 h.
3
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10.1002/adsc.201800362
Advanced Synthesis & Catalysis
Scheme 2. Gram-Scale Preparation of 3aa and Conversion
of the Products
Based on the preliminary mechanistic experiments
and literature precedents, a plausible mechanism is
proposed (Scheme 4). Firstly, benzoylacetonitrile was
activated by Rh(III) catalyst to give intermediate A,
followed by the concerted metalation-deprotonation
(CMD) pathway to obtain a five membered
rhodacycle B, which is trapped by the ylide
compound 2a to form the rhodium-carbene C upon
extrusion of DMSO. Then, migratory insertion of the
carbene into the Rh-aryl bond furnishes the six-
membered rhodacyclic intermediate D, and
protonolysis of the Rh-alkyl bond by HOAc leads to
intermediate E. The catalytic cycle is completed
through the ralease of Rh catalysis to give the key
intermediate F, which underwent a sequential aldol
condensation and intramolecular double bond shift to
form the desired product 3aa.
Scheme 4. Proposed Mechanism
Conclusion
In summary, we developed an efficient Rh(III)-
catalyzed annulation of benzoylacetonitriles with
sulfoxonium ylides to provide a concise synthetic
strategy for 3-substituted naphthols, in which aryl,
heterocyclic and alkyl groups in sulfoxonium ylides
are tolerated. More importantly, we further
implemented derivatization of 1-naphthols to
synthesize fused tricyclic scaffolds naphtho[1,8-
bc]pyrans and propranolol derivatives via some
simple operations.
Experimental Section
General precedure for the Synthesis of the Target
Naphthols 3 and 4 (3aa as an example)
A pressure tube was charged with [Cp*RhCl2]2 (4 mol %,
2.5
mg),
CsOAc
(0.2
mmol,
19.2
mg),
benzoylacetonitrile1a (0.1 mmol, 14.5 mg), sulfoxonium
ylide 2a (0.12 mmol, 23.6 mg) and DCE (3 mL). The
reaction mixture was stirred at 50 oC for 6 h. After that, the
solvent was removed under reduced pressure and the
residue was purified by silica gel chromatography using
DCM/MeOH to afford the product 3aa, white solid, 19.8
1
mg, yield 81%. HNMR (400 MHz, DMSO-d6) δ 11.59 (s,
1H), 8.40 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H),
7.75-7.71 (t, 1H), 7.68-7.62 (m, 3H), 7.58-7.53 (m, 3H),
7.51 (dd, J = 10.6, 3.8 Hz, 1H). 13CNMR (125 MHz,
DMSO-d6) δ 93.5, 116.4, 119.7, 122.0, 122.6, 125.9, 127.6,
127.7, 127.8, 128.2, 129.0, 134.8, 137.9, 138.5, 159.1.
HRMS (ESI) m/z: calculated for C17H10NO [M-H]-:
244.0768, found: 244.0765.
Scheme 3. Preliminary Mechanistic Studies
Synthesis of 8-(4-methoxyphenyl)-2,3-diphenyl-
benzo[de]chromene-9-carbonitrile (6)
A dried schlenk tube equipped with a stir bar was loaded
with the naphthol 4ad (59.2 mg, 0.2 mmol), 1,2-
diphenylethyne (17.8 mg, 0.1 mmol), [Cp*RhCl2]2 (2.5
mg, 0.004 mmol), Cu(OAc)2·H2O(1.8 mg, 0.01 mmol) and
toluene (3 mL) under the atmosphere of O2 (1 atm). The
o
tube was then stirred at 100 C for 12 h. After cooling
down to room temperature, the solvent was evaporated in
vacuum, the residue was purified through flash column
chromatography on silica gel to afford the pure product 6,
4
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10.1002/adsc.201800362
Advanced Synthesis & Catalysis
1
yellow solid, 16.7 mg, yield: 55%. HNMR (400 MHz,
CDCl3) δ 7.60 (d, J = 8.7 Hz, 2H), 7.48-7.35 (m, 7H),
7.29-7.25 (m, 4H), 7.24-7.21 (m, 2H), 7.08-7.02 (m, 2H),
6.65 (d, J = 6.6 Hz, 1H), 3.88 (s, 3H). 13CNMR (125 MHz,
CDCl3) δ 160.0, 157.8, 149.4, 141.4, 135.9, 134.6, 132.7,
132.1, 131.2, 130.9, 130.7, 130.1, 129.5, 129.0, 128.9,
128.2, 128.0, 124.0, 120.4, 119.6, 118.4, 117.4, 116.1,
114.1, 90.8, 55.4. HRMS (ESI) m/z: calculated for
C32H22NO2 [M+H]+: 452.0334, found: 452.0335.
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Synthesis of 1-(2-hydroxy-3-(isopropylamino)
propoxy)-3-methyl-2-naphthonitrile (8)
The naphthol 4aj (1 equiv, 50.0 mg) was dissolved in
acetone (3 mL), and potassium carbonate (2 equiv, 75.4
mg) was added in a microwave tube. After epichlorohydrin
(2 equiv, 50.5 mg) was added, the tube was sealed and
irradiated in a microwave reactor for 20 min at 100 oC with
100 W. After TLC control, purification with flash
chromatography was performed (40.5 mg, yield: 62%).The
oxirane 7 (1 equiv, 20.0 mg) and isopropylamine (10 equiv,
50 mg) and calcium trifluoromethanesulfonate (0.5 equiv,
14.1 mg) were added in a microwave tube with seal. The
mixtures were irradiated in a microwave reactor for 25 min
[5] a) L. Lan, C. Appelman, A. R. Smith, J. Yu, S. Larsen,
R. T. Marquez, H. Liu, X. Wu, P. Gao, A. Roy, A.
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o
(100 W, 100 C) with the sealed tube. After TLC control,
the reaction mixture was purified by flash chromatography
to afford oil product 8: colorless oil, 23.0 mg, yield 92%.
1HNMR (400 MHz, CDCl3) δ 8.12 (d, J = 8.3 Hz, 1H),
7.65 (d, J = 8.2 Hz, 1H), 7.50 (t, J = 7.5 Hz, 1H), 7.45-7.39
(m, 1H), 7.34 (s, 1H), 4.82-4.72 (m, 1H), 4.32 (d, J = 4.0
Hz, 2H), 3.62-3.42 (m, 3H), 2.50 (s, 3H), 1.57-1.43 (m,
6H). 13CNMR (125 MHz, CDCl3) δ 159.9, 136.2, 135.4,
129.5, 127.4, 126.8, 125.2, 124.3, 122.7, 116.3, 103.1, 66.2,
51.9, 48.1, 20.6, 19.1, 18.9. HRMS (ESI) m/z: calculated
for C18H23N2O2 [M+H]+: 299.1754, found: 299.1755.
Acknowledgements
[6] a) R.-Q. Xu, Q. Gu, S.-L. You, Angew. Chem. Int. Ed.
2017, 56, 7252-7256; b) L. Pu, Acc. Chem. Res. 2014,
47, 1523-1535; c) T. Dohi, N. Takenaga, T. Nakae, Y.
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We are grateful to the National Natural Science Foundation of
China (No. 21672232, 21632008, 81620108027) and Institutes
for Drug Discovery and Development, Chinese Academy of
Sciences (No. CASIMM0120162018).
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FULL PAPER
Rh(III)-Catalyzed C-H Activation of
Benzoylacetonitriles and Cyclization with
Sulfoxonium Ylides to Naphthols
Adv. Synth. Catal. Year, Volume, Page – Page
Chaofan Zhou a,b, Feifei Fangb, Yilang Chengb,
Yazhou Lib, Hong Liub,* and Yu Zhoub,*
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