Construction of C–O bond via cross-dehydrogenative coupling of sp [ 3] C–H bond with phenols catalyzed by copper porphyrin

Article abstract of DOI:10.1016/j.tet.2020.131569

Copper porphyrin-catalyzed construction of ether bond by cross-dehydrogenative coupling of sp [3] C–H bond with phenols bearing electron-withdrawing groups (EWG) was described for the first time. A broad range of substrates afforded different acetals in m

Full text of DOI:10.1016/j.tet.2020.131569

Tetrahedron xxx (xxxx) xxx
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Construction of CeO bond via cross-dehydrogenative coupling of sp
[3] CeH bond with phenols catalyzed by copper porphyrin
Shuang Yang a, Ming-Feng Xiong a, Wan-Qun Tian a, Hao Zhang a, Xin-Yan Xiao a,
,
, **
Hai-Yang Liu a *, Chi-Kwong Chang b
a Department of Chemistry, Key Laboratory of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou,
510641, China
b Department of Chemistry, Michigan State University, E. Lansing, MI, 48824, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Copper porphyrin-catalyzed construction of ether bond by cross-dehydrogenative coupling of sp [3] CeH
bond with phenols bearing electron-withdrawing groups (EWG) was described for the first time. A broad
range of substrates afforded different acetals in moderate to excellent yields with good functional group
tolerance. The developed method is not only suitable for phenol substrates with ortho-directing groups,
but also suitable for those phenol without ortho-directing groups. Significantly, a high turnover number
(TON) up to 7300 was achieved in gram-level test.
Received 6 July 2020
Received in revised form
28 August 2020
Accepted 31 August 2020
Available online xxx
© 2020 Elsevier Ltd. All rights reserved.
Keywords:
Cross-dehydrogenative coupling
Phenolic etherification
Porphyrin
Copper
1. Introduction
Metalloporphyrins [9] are good catalysts in many reactions such
as cyclopropanation [10], oxidation [11], olefination [12], carbene
Cross-dehydrogenative coupling (CDC) reactions play an
important role for construction of C-X (X ¼ C, O, N) bonds in organic
synthesis [1a,1b,1c,1d]. This reaction does not need the pre-
functionalization of starting materials, which makes it a conve-
nient, atom economical and environmentally benign method. CeO
bond moiety is a vital building block in organic compounds and
natural products [2]. Although significant progress has been ach-
ieved in the construction of CeC bond via CDC reaction
[3a,3b,3c,3d], the formation of CeO bond by CDC reaction still re-
mains a considerable challenge [4a,4b,4c]. The esterification [5] and
formamidation [6a,6b,6c] of phenol substrates with sp [2] CeH of
aldehyde and formamide have been achieved by CDC reaction.
Recently, the etherification of sp [3] CeH of ethers with phenol
have also been achieved by using copper and/or iron catalysts
(Scheme 1, a) [7a,7b,7c]. In addition, heterogeneous catalysts such
as Cu-MOFs and nanosized copper were also successfully applied to
oxidative CeO coupling of phenols with cyclic ether [8a,8b,8c,8d].
[13] and nitrene [14] CeH insertion reactions. However, reports on
the application of metalloporphyrin in CDC reactions are scarce. In
2013, Che and his co-workers had achieved CDC reaction of tertiary
amines and diethyl phosphite or dimethyl malonate by using Pd (II)
porphyrin catalyst under irradiation [15]. Copper porphyrin-
catalyzed aerobic oxidative coupling of terminal alkynes was also
proved high TON [16]. Manganese Tetrakis(ethoxycarbonyl)
porphyrin (TECP) complex is a robust catalyst in the oxidation re-
action due to the electron-deficient virtue of this porphyrin ligand
[17]. Recently, we found copper and iron TECP complexes exhibited
excellent activity in the CDC reactions between carboxylic acid and
cyclic ether [18a,18b]. When the benzoic acid derivative bearing a
phenolic hydroxyl group was used as substrate, the hydroxyl group
may couple with 1, 4-dioxane directly to form ether bonds with 36%
yield [18b]. Based on this observation, we herein wish to report the
systematic investigations of CDC reactions between phenol de-
rivatives and cyclic ether (scheme 1, b) by using a series of metal
TECP complexes (M-TECP) (Fig.1). It was demonstrated that CuTECP
exhibited excellent activity in CDC reaction of phenols and cyclic
ether. To our surprise, compared with previous reports [7a,7b,7c],
ortho-directing groups are not compulsory for phenol substrates in
the current catalytic system, which implies Cu(II) porphyrin
* Corresponding author.
** Corresponding author.
E-mail address: chhyliu@scut.edu.cn (H.-Y. Liu).
https://doi.org/10.1016/j.tet.2020.131569
0040-4020/© 2020 Elsevier Ltd. All rights reserved.
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

2
S. Yang et al. / Tetrahedron xxx (xxxx) xxx
Table 1
Optimization of reaction conditionsa.
Entry
Cat. (mol %)
Oxidant (equiv)
Yieldb
1
2
3
4
5
6
7
8
CuTECP (5)
CuTECP (5)
CuTECP (5)
CuTECP (5)
CuTECP (5)
CuTECP (5)
CuTECP (5)
FeTECPCl (5)
NiTECP (5)
PdTECP (5)
CoTECP (5)
AgTECP (5)
MnTECPCl (5)
ZnTECP (5)
CuTPP (5)
CuF20TPP (5)
CuSO4 (5)
DTBP (3.5)
TBHP (3.5)
m-CPBA (3.5)
H2O2 (3.5)
PhI(OAc)2 (3.5)
Oxone (3.5)
DDQ (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
DTBP (3.5)
e
97
trace
N.D.
N.D.
N.D.
N.D.
N.D.
22
trace
N.D.
N.D.
13
9
trace
67
61
8
Scheme 1. CDC reaction of phenol derivatives and cyclic ethers.
9
10
11
12
13
14
15c
16d
17
18
19
e
11
N.D.
CuTECP (5)
Fig. 1. The structure of metal TECP, CuTPP and CuF20TPP.
a
Reaction conditions: methyl 4-hydroxybenzoate (0.5 mmol), 1,4-dioxane
(2 mL), catalyst, oxidant, 120 C, 12 h.
b
Yields were determined by 1H NMR spectroscopy using toluene as an internal
catalyzed reaction goes via a different pathway in which the coor-
dination interaction between Cu center atom and directing group is
not a key factor controlling the reaction.
standard.
c
(tetraphenylporphyrinato)copper(II).
tetrakis(perfluorophenyl)porphyrinato)copper(II). N.D.
d
¼
Not detected.
DTBP
¼
di-tert-butyl peroxide. TBHP tert-butyl hydroperoxide (5e6 M, in
¼
decane). m-CPBA ¼ 3-chloroperbenzoic acid. H2O2 (30% in H2O). Oxone ¼ potassium
2. Results and discussion
peroxymonosulfate.
Initially, methyl 4-hydroxybenzoate 1a and 1,4-dioxane 1b were
used as the model substrates and treated with various oxidant
using CuTECP as catalyst (Table 1, entry 1e7). DTBP oxidant gave the
highest yield (97%) of the desired product. Motivated by this result,
other M-TECP catalysts (M ¼ Fe, Ni, Pd, Co, Ag, Mn, Zn) were also
investigated (Table 1, entry 8e14). It turned out that most other M-
TECP complexes were inactive except for FeTECPCl. Tetraki-
The reaction was not very compatible with halogen-substituted
phenols (3ua, 3xa-3za). Nitro phenols did not work under
optimal condition, because the nitro group is not compatible with
the oxidative conditions, it may quench oxygen radical [20a,20b]
and result the termination of the reaction (3
aa). The hydroxypyr-
idine substrate provided 38% yield (3 a), indicating the current
b
system may be extended to other aromatic hydroxyl substrates.
Moreover, the parent unsubstituted phenol did not react with 1,4-
dioxane, suggesting the necessity of EWG for this CDC reaction.
To further investigate the scope of phenol in this reaction, the
polysubstituted phenols bearing an EWG were tested (Table 3). It
s(phenylporphyrinato)copper(II)
(CuTPP)
and
tetrakis(per-
fluorophenyl)porphyrinato)copper(II) (CuF20TPP) gave moderate
yields (Table 1, entry 15e16), while the copper sulfate salt was
nearly inactive for the reaction (Table 1, entry 17). DTBP itself might
give 11% yield product (Table 1, entry 18). Besides, CuTECP could not
yield the desired product in the absence of oxidant (Table 1, entry
19). Other factors such as reaction time and temperature (Table S1)
were tested to furnish the reaction optimization (Table 1, entry 1).
With the optimized conditions in hand, we explored the scope
of phenol substrates with 1,4-dioxane subsequently. It was re-
ported that 29% yield could be obtained by coupling p-methyl-
phenol with tetrahydrofuran [19]. In our cases, the target products
could not be obtained when the phenols bear electron-donating
groups (EDG) such as methyl, methoxy, hydroxyl, tertiary butyl
and amino in current system (Scheme S1). In contrast, the phenols
with mono substituted electron-withdrawing groups (EWG) fur-
nished target products in moderate to excellent yields (Table 2).
This indicated that the reaction was sensitive to electronic structure
of phenols. Phenols bearing methoxycarbonyl group at different
positions of the aromatic moiety gave the corresponding acetals in
excellent yields even up to 99% (3aa-3ca). The phenols bearing
formyl, acetyl, cyano or trifluoromethyl group at ortho position of
the aromatic moiety gave higher yields than those at the para- and
meta-position (3da-3oa). Furthermore, the phenols whose ortho-
site was amide-group might also yield moderate yields (3qa-3sa).
̊
turned out that methoxy substituted phenols containing an EWG
could give corresponding products in moderate to excellent yields
(3a′a, 3b′a, 3d′a and 3i′a). While methyl or halogen substitution
will decrease the yields of corresponding acetals (3c′a, 3f′a, 3j′a-
3m′a, 3o′a-3p′a). Moreover, The product methyl 2,4-bis((1,4-
dioxan-2-yl)oxy)benzoate was obtained by coupling two phenolic
hydroxyl groups with 1,4-dioxane (3e′a). To our delight, the 1-
hydroxy-2-naphthaldehyde provided 99% isolated yield of corre-
sponding product without any by-products (3g′a). Significantly, the
tolerance of functional groups such as ester, formyl, cyano and
alkoxy groups is beneficial for further synthetic manipulation.
Subsequently, the scope of ethers was also explored (Table 4).
Tetrahydrofuran offered desired product in 90% yield (3 ab)
whereas other cyclic ethers generated corresponding products in
low yields (3ac-3ad, 3ah) probably due to heterocycle ring cleav-
age. Selective reaction products along with unidentifiable by-
products were provided by asymmetric cyclic ethers (3ac, 3ah),
which was similar to previous report [21]. To our satisfaction, the
reaction was also compatible with aliphatic ethers albeit with low
yields (3ae-3af). Meantime, the reaction of 1,2-dimethoxyethane
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

S. Yang et al. / Tetrahedron xxx (xxxx) xxx
3
Table 2
Substrate scope of phenola.
Table 3
Substrate scope of polysubstituted phenola.
yielded the isomers 3 ag and 3 ag′ in a ratio of 2:1 with a 30%
overall yield. Additionally, other type of CeH bond substrates were
also explored (3ai-3ak). The formamidation of N,N-
dimethylformamie with phenol could be achieved and gave
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

4
S. Yang et al. / Tetrahedron xxx (xxxx) xxx
Table 4
Substrate scope of ethera.
desired product 3aj. Occasionally, we obtained the crystal of 3aj and
confirmed its structure by X-ray crystallography (Fig. S7). Unfor-
tunately, 1,3-benzodioxole, anisole and pyrrolidine were inert un-
der optimum condition (3 al-3an).
Encouraged by the excellent scope of substrates obtained under
current catalytic system, a gram-level reaction experiment was
performed by using methyl 4-hydroxybenzoate and 1,4-dioxane as
starting materials. As a result, turnover number (TON) could reach
7300 (73% yield) at 0.01 mol % CuTECP catalyst (Scheme 2),
demonstrating that the current system had great potential in in-
dustry utility.
In order to clarify the reaction mechanism, free radical scav-
enger and deuterium isotope experiments were performed
(Scheme 3). No product could be detected when free radical in-
hibitors 2,2,6,6-teramethylpyridine (TEMPO) or butylated hydrox-
ytoluene (BHT) was added to the reaction system (Scheme 3, a),
which indicated that the reaction proceeded via a radical pathway.
Fig. 2 showed the electron paramagnetic resonance (EPR) spectra of
reaction mixture. Except for the EPR signal of CuTECP catalyst, free
radical EPR signal centered at g ¼ 2.0 could be observed clearly,
further conforming the generation of carbon radical in this CDC
reaction. Moreover, when radical capturer TMPEO was added to the
reaction system, TEMPO-1,4-dioxane adduct (Scheme 3, b) could be
detected by ESI-MS, demonstrating that the existence of 1,4-
dioxane radical. The kinetic isotope effect (KIE) values obtained
from both competitive reaction (KH/KD ¼ 4.6) and parallel reaction
(KH/KD ¼ 2.2) were larger than 2 (Scheme 3, c), indicating that the
Scheme 3. Mechanistic investigation. a) and b) Radical inhibition experiment. c) Ki-
netic isotope study.
Fig. 2. EPR spectra of reaction mixture (red) and CuTECP catalyst (blue).
Scheme 2. Gram-lever reaction.
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
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S. Yang et al. / Tetrahedron xxx (xxxx) xxx
5
reaction mechanism details are still need to be elucidated.
4. Experimental section
4.1. General information
All the reagents were commercial grade and used without pu-
rification if not mentioned otherwise. All metalloporphyrins were
prepared according to our reported procedure and spectral data
were found identical to previous reports [18a]. Thin-layer chro-
matography (TLC) was carried out on Merck 60 F254 precoated,
glass silica gel plates which were visualized with ultraviolent light.
1H, 13C and 19F NMR spectra were recorded on Bruker Ascend™ 500
and Bruker Avance 400M NMR spectrometers. An Agilent 6210 ESI
mass spectrometer was used to obtain high resolution mass (HR-
MS) spectra. EPR spectra was recorded at room temperature on EPR
spectrometer operated at Bruker ELEXSYS-II E500 CW-EPR spec-
trometer. Single-crystal X-ray crystallography was collected at
100 K on a Rigaku Oxford Diffraction Supernova Dual Source, Cu at
Scheme 4. Proposed reaction mechanism.
C(sp [3])-H bond cleavage of 1,4-dioxane is the kinetic rate-
determining step, which was similar to previous published results
[21].
Zero equipped with an AtlasS2 CCD using Cu Ka radiation.
4.2. General procedure for the synthesis of 3aa-3wa, 3a0a-3p0a and
3 ab-3ak: preparation of 3aa as a representative example
Based on these observations and previous literatures [22], a
plausible reaction path way is proposed in Scheme 4. First,
CuTECP(II) assists the homolysis of DTBP to generate tert-butoxyl
radical and tBuO-Cu(III)TECP complex A [22]. Complex A subse-
quently reacts with methyl 4-hydroxybenzoate B to produce C in-
termediate and releases tert-butanol (t-BuOH). Free radical D is
generated from the dehydrogenative reaction of 1,4-dioxane and
tert-butoxyl radical. The reaction of free radical species D with in-
termediate C furnished the desired product E and regenerate the
active Cu(II)TECP catalyst to furnish the catalytic cycle. It should be
pointed out that it is not popular for a alkyl radical attacks a Cu(III)
species in the copper chemistry. Although in KharascheSosnovsky
reaction, the allylic radical may attack the Cu(II) to form Cu(III)-
allylic intermediate via BeckwitheZavitsas pathway [23]. In our
cases, the initial catalyst is Cu(II) and the intermediate is a Cu(III)
species. Perhaps the porphyrin ligand has four N donor atoms, and
porphyrin Cu(III) center has more electron density and may act like
Cu(II) center. So, we assume porphyrin Cu(III) may still be attacked
by alkyl radical [24]. Compared with previous reported systems
which limited phenols bearing ortho-directing group [7b,7c,8b,8d],
the current reaction system has the advantage of more extended
scope of phenol substrates. Furthermore, the electron-rich phenols
are inefficient under current system, which is probably due to the
acidity of electron-rich phenols is weaker than that of electron-
deficient phenols, thus it does not favor the conversion of inter-
mediate A to C (Scheme 4). Also, for intermediate C, the electron-
rich group on the phenol ring will enhance the CueO coordina-
tion bond which may hinder the release of product E.
CuTECP (16.5 mg, 0.025 mmol, 5 mol %) and methyl 4-
hydroxybenzoate (1a, 76 mg, 0.5 mmol, 1.0 equiv) were added to
a Schlenk tube equipped with a magnetic stir bar. Then,1,4-dioxane
(1b, 2 mL) and DTBP (di-tert-butyl peroxide, 1.75 mmol, 333 mL, 3.5
equiv) were added. The resulting reaction mixture was stirring at
120 C for 12 h. The reaction mixture was cooled to room temper-
ature and the solvent was removed under vacuum yielding the
crude product, which was purified by column chromatography
(hexane (Hex)/ethyl acetate (EA), 10/1) to afford the desired prod-
uct 3aa.
4.3. Procedure for the gram level reaction of 3aa
250 mL round flask equipped with a magnetic stir bar was
selected as reactor. CuTECP (0.66 mg, 0.001 mmol, 0.01 mol %) and
methyl 4-hydroxybenzoate (1a, 1.52 g, 10 mmol) were added first.
Then, 1,4-dioxane (2a, 40 mL) and DTBP (35 mmol, 6660 mL) were
added. The resulting reaction mixture was stirred at 120 C for 72 h.
After the reaction mixture was cooled to room temperature, the
solvent was removed under vacuum and yielded the crude product.
It was purified by column chromatography on silica gel (Hex/EA, 10/
1) to produce the desired product 3aa as a white solid (1.74 g, 73%
yield, TON ¼ 7300).
4.4. Procedure for free radical capture experiment
CuTECP (16.5 mg, 0.025 mmol, 5 mol %) and methyl 4-
hydroxybenzoate (1a, 76 mg, 0.5 mmol, 1.0 equiv) were added to
a Schlenk tube equipped with a magnetic stir bar. Then,1,4-dioxane
3. Conclusion
In conclusion, we have developed an efficient copper porphyrin-
catalyzed CeO bond formation via CDC reaction of sp [3] CeH
bonds with phenols bearing electron-withdrawing groups. The
reaction yielded corresponding acetal products in moderate to
excellent yield. Importantly, the ortho-directing groups were not
compulsory for phenol substrates in current system, which was
different from all those previously published CDC catalytic system
of phenols. Moreover, the gram-level reaction demonstrated a high
TON up to 7300, demonstrating the advantage of copper porphyrin
catalyst and the industrial utility of the developed synthetic
method. Preliminary mechanistic investigations revealed that the
current reactions proceeded via a free-radical pathway and more
(2a, 2 mL), DTBP (1.75 mmol, 333 mL, 3.5 equiv) and 2,2,6,6-
̊
teramethylpyridine N-oxide (TEMPO, 352 mg, 4.5 equiv) or butyl-
ated hydroxytoluene (BHT, 496 mg, 4.5 equiv) were added. The
resulting reaction mixture was stirred at 120 C for 12 h. No desired
product 3aa was detected by TLC.
4.5. Procedure for control experiment kinetic isotopic effect
4.5.1. Intermolecular competition KIE experiment
CuTECP (16.5 mg, 0.025 mmol, 5 mol %) and methyl 4-
hydroxybenzoate (1a, 76 mg, 0.5 mmol, 1.0 equiv) were added to
a Schlenk tube equipped with a magnetic stir bar. Then,1,4-dioxane
̊
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
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6
S. Yang et al. / Tetrahedron xxx (xxxx) xxx
(1 mL), 1,4-dioxane-d8 (1 mL) and DTBP (1.75 mmol, 333
mL, 3.5
4.5.8. 3-((1,4-Dioxan-2-yl)oxy)benzaldehyde (3fa)
equiv) were added. The resulting reaction mixture was stirred at
120 C for 12 h. The reaction mixture was cooled to room temper-
ature and the solvent was removed under vacuum yielding the
crude product, which was purified by column chromatography
(Hex/EA, 10/1) to afford the desired product.
(18 mg, 17%) as a yellow oil, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 9.97 (s, 1H), 7.59 (s, 1H),
7.54 (d, J ¼ 7.4 Hz, 1H), 7.46 (t, J ¼ 7.8 Hz, 1H), 7.34 (d, J ¼ 8.1 Hz, 1H),
5.36 (s, 1H), 4.16e4.08 (m, 1H), 3.89 (s, 2H), 3.81 (d, J ¼ 3.6 Hz, 2H),
3.62 (d, J ¼ 11.8 Hz, 1H). 13C NMR (101 MHz, CDCl3)
d 192.0, 157.4,
138.0, 130.3, 124.3, 123.3, 116.2, 93.7, 77.5, 77.2, 76.8, 68.7, 66.3, 61.3.
HR-MS (ESI) calcd for C11H12NaO4 [MþNa]þ 231.0628, found:
231.0629.
4.5.2. Intermolecular parallel KIE experiment
CuTECP (16.5 mg, 0.025 mmol, 5 mol %) and methyl 4-
hydroxybenzoate (1a, 76 mg, 0.5 mmol, 1.0 equiv) were added to
a Schlenk tube equipped with a magnetic stir bar. Then, 1,4-dioxane
4.5.9. 1-(4-((1,4-Dioxan-2-yl)oxy)phenyl)ethan-1-one (3ga)
(2 mL) or 1,4-dioxane-d8 (2 mL) and DTBP (1.75 mmol, 333
m
L, 3.5
(52 mg, 47%) as a colorless solid, Hex/EA as the eluent (Hex/
equiv) were added. The resulting reaction mixture was stirred at
120 C for 12 h. Mixing the two reaction mixtures together after it
cooled to room temperature, the solvent was removed under vac-
uum yielding the crude product, which was purified by column
chromatography (Hex/EA, 10/1) to afford the desired product.
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
7.93 (d, J ¼ 8.2 Hz, 2H),
d
7.11 (d, J ¼ 8.2 Hz, 2H), 5.37 (s, 1H), 4.10 (dt, J ¼ 12.0, 6.1 Hz, 1H),
3.93e3.84 (m, 2H), 3.82e3.75 (m, 2H), 3.60 (d, J ¼ 11.8 Hz, 1H), 2.55
(s, 3H). 13C NMR (101 MHz, CDCl3)
d 196.6, 160.3, 131.2, 130.3, 115.7,
93.0, 77.2, 76.8, 76.5, 68.3, 65.9, 60.9, 26.2. HR-MS (ESI) calcd for
C
12H15O4 [MþH]þ 223.0965, found: 223.0962.
4.5.3. Methyl 4-((1,4-dioxan-2-yl)oxy)benzoate (3aa)
(101 mg, 85%) as a white solid, Hex/EA as the eluent (Hex/
4.5.10. 1-(2-((1,4-Dioxan-2-yl)oxy)phenyl)ethan-1-one (3ha) [7a]
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.98 (d, J ¼ 8.3 Hz, 2H),
(99 mg, 89%) as a white solid, Hex/EA as the eluent (Hex/
7.09 (d, J ¼ 8.3 Hz, 2H), 5.35 (s, 1H), 4.09 (dd, J ¼ 11.9, 6.0 Hz, 1H),
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.71 (d, J ¼ 7.7 Hz, 1H),
3.87 (s, 5H), 3.79 (d, J ¼ 4.3 Hz, 2H), 3.59 (d, J ¼ 11.8 Hz,1H). 13C NMR
7.41 (t, J ¼ 7.8 Hz, 1H), 7.16 (d, J ¼ 8.4 Hz, 1H), 7.03 (t, J ¼ 7.5 Hz, 1H),
5.38 (s, 1H), 4.07 (dt, J ¼ 12.0, 6.1 Hz, 1H), 3.88 (s, 2H), 3.78 (dd,
J ¼ 5.0, 1.8 Hz, 2H), 3.60 (d, J ¼ 11.5 Hz, 1H), 2.67 (s, 3H). 13C NMR
(101 MHz, CDCl3)
d 166.8, 160.5, 131.6, 124.0, 116.0, 93.3, 77.5, 77.2,
76.8, 68.6, 66.2, 61.2, 52.0. HR-MS (ESI) calcd for C12H15O5 [MþH]þ
239.0914, found: 239.0915.
(101 MHz, CDCl3) d 200.1, 156.0, 133.8, 130.7, 129.4, 122.3, 115.4,
93.9, 77.8, 77.5, 77.2, 68.9, 66.4, 61.7, 32.5. HR-MS (ESI) calcd for
C
̊
4.5.4. Methyl 2-((1,4-dioxan-2-yl)oxy)benzoate (3ba)
12H15O4 [MþH]þ 223.0965, found: 223.0962.
(111 mg, 93%) as a white solid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.74 (d, J ¼ 7.6 Hz, 1H),
4.5.11. 1-(3-((1,4-Dioxan-2-yl)oxy)phenyl)ethan-1-one (3ia)
7.39 (t, J ¼ 7.6 Hz, 1H), 7.18 (d, J ¼ 8.3 Hz, 1H), 7.03 (t, J ¼ 7.5 Hz, 1H),
5.19 (s, 1H), 4.17 (dt, J ¼ 11.4, 5.6 Hz, 1H), 3.90 (d, J ¼ 11.8 Hz, 1H),
3.85e3.80 (m, 4H), 3.73 (d, J ¼ 5.9 Hz, 2H), 3.57 (d, J ¼ 11.4 Hz, 1H).
(37 mg, 33%) as a yellow oil, Hex/EA as the eluent (Hex/
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
d 7.67 (s, 1H), 7.61 (d,
J ¼ 7.6 Hz, 1H), 7.39 (t, J ¼ 7.9 Hz, 1H), 7.29 (d, J ¼ 8.0 Hz, 1H), 5.36 (s,
1H), 4.13 (dt, J ¼ 11.9, 6.0 Hz, 1H), 3.89 (s, 2H), 3.81 (dd, J ¼ 4.9,
1.8 Hz, 2H), 3.62 (d, J ¼ 12.4 Hz, 1H), 2.59 (s, 3H). 13C NMR (101 MHz,
13C NMR (101 MHz, CDCl3)
d 166.5, 156.4, 133.3, 131.4, 122.4, 122.3,
118.5, 95.5, 77.5, 77.2, 76.8, 68.5, 66.1, 61.5, 52.1, 52.0. HR-MS (ESI)
calcd for C12H15O5 [MþH]þ 239.0914, found: 239.0910.
CDCl3) d 197.8, 156.9, 138.7, 129.8, 122.3, 121.5, 115.9, 93.7, 77.5, 77.2,
76.8, 68.7, 66.2, 61.3, 26.8. HR-MS (ESI) calcd for C12H15O4 [MþH]þ
4.5.5. Methyl 3-((1,4-dioxan-2-yl)oxy)benzoate (3ca)
223.0965, found: 223.0967.
̊
(118 mg, 99%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.75 (s, 1H), 7.70 (d,
4.5.12. 4-((1,4-Dioxan-2-yl)oxy)benzonitrile (3ja)
J ¼ 7.6 Hz, 1H), 7.36 (t, J ¼ 7.9 Hz, 1H), 7.27 (d, J ¼ 8.1 Hz, 1H), 5.35 (s,
(85 mg, 83%) as a yellow solid, Hex/EA as the eluent (Hex/
1H), 4.13 (dt, J ¼ 11.8, 5.9 Hz, 1H), 3.89 (d, J ¼ 9.9 Hz, 5H), 3.82e3.78
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
7.57 (d, J ¼ 8.3 Hz, 2H),
d
(m, 2H), 3.61 (d, J ¼ 11.8 Hz, 1H). 13C NMR (101 MHz, CDCl3)
d
166.8,
7.12 (d, J ¼ 8.2 Hz, 2H), 5.33 (s,1H), 4.06 (dt, J ¼ 12.1, 6.2 Hz,1H), 3.87
156.7,131.6, 129.6,123.4,121.5,117.2, 93.6, 77.5, 77.2, 76.8, 68.7, 66.2,
61.2, 52.3. HR-MS (ESI) calcd for C12H14NaO5 [MþNa]þ 261.0733,
found: 261.0736.
(p, J ¼ 12.3 Hz, 2H), 3.78 (d, J ¼ 6.1 Hz, 2H), 3.58 (d, J ¼ 11.7 Hz, 1H).
13C NMR (101 MHz, CDCl3)
d 160.5, 134.5, 119.5, 117.5, 105.8, 93.8,
78.0, 77.6, 77.3, 68.9, 66.6, 61.6. HR-MS (ESI) calcd for C12H11NNaO3
[MþNa]þ 228.0631, found: 228.0630.
4.5.6. 4-((1,4-Dioxan-2-yl)oxy)benzaldehyde (3da)
(44 mg, 42%) as a yellow solid, Hex/EA as the eluent (Hex/
4.5.13. 2-((1,4-Dioxan-2-yl)oxy)benzonitrile (3ka)
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
9.90 (s, 1H), 7.85 (d,
(92 mg, 90%) as a colorless solid, Hex/EA as the eluent (Hex/
J ¼ 8.2 Hz, 2H), 7.19 (d, J ¼ 8.2 Hz, 2H), 5.40 (s, 1H), 4.11 (dt, J ¼ 12.0,
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.58 (d, J ¼ 7.7 Hz, 1H),
6.2 Hz, 1H), 3.95e3.85 (m, 2H), 3.82 (d, J ¼ 6.0 Hz, 2H), 3.61 (d,
7.54 (t, J ¼ 8.1 Hz, 1H), 7.26 (d, J ¼ 8.5 Hz, 1H), 7.09 (t, J ¼ 7.6 Hz, 1H),
5.37 (s, 1H), 4.22e4.12 (m, 1H), 3.97 (d, J ¼ 12.0 Hz, 1H), 3.90 (d,
J ¼ 11.8 Hz, 1H). 13C NMR (101 MHz, CDCl3)
d 191.0, 161.7, 132.0,
131.1, 116.6, 93.4, 77.5, 77.2, 76.8, 68.6, 66.2, 61.2. HR-MS (ESI) calcd
J ¼ 12.0 Hz, 1H), 3.81 (d, J ¼ 4.7 Hz, 2H), 3.64 (d, J ¼ 11.8 Hz, 1H). 13
C
for C11H12NaO4 [MþNa]þ 231.0628, found: 231.0633.
NMR (101 MHz, CDCl3) d 158.8, 134.6, 133.9, 122.6, 116.4, 116.1,
103.5, 94.8, 77.8, 77.5, 77.2, 68.4, 66.1, 61.7. HR-MS (ESI) calcd for
4.5.7. 2-((1,4-Dioxan-2-yl)oxy)benzaldehyde (3ea) [7b]
C
12H11NNaO3 [MþNa]þ 228.0631, found: 228.0630.
(56 mg, 54%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
10.55 (s, 1H), 7.85 (d,
4.5.14. 3-((1,4-Dioxan-2-yl)oxy)benzonitrile (3la)
J ¼ 7.7 Hz, 1H), 7.53 (t, J ¼ 7.8 Hz, 1H), 7.22 (d, J ¼ 8.5 Hz, 1H), 7.09 (t,
J ¼ 7.5 Hz, 1H), 5.40 (s, 1H), 4.12 (dt, J ¼ 11.9, 6.0 Hz, 1H), 3.97e3.87
(m, 2H), 3.83e3.78 (m, 2H), 3.63 (d, J ¼ 11.9 Hz, 1H). 13C NMR
(35 mg, 34%) as a white solid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 7.42e7.35 (m, 2H), 7.30
(d, J ¼ 6.9 Hz, 2H), 5.29 (s, 1H), 4.13e4.05 (m, 1H), 3.88 (s, 2H), 3.80
(101 MHz, CDCl3)
d 189.8, 189.7, 159.2, 135.9, 128.3, 125.8, 122.3,
(dd, J ¼ 4.7, 2.6 Hz, 2H), 3.61 (dt, J ¼ 11.7, 2.7 Hz, 1H). 13C NMR
115.6, 93.9, 77.5, 77.2, 76.8, 68.5, 66.1, 61.5. HR-MS (ESI) calcd for
(101 MHz, CDCl3) d 156.9, 130.5, 125.9, 121.6, 119.7, 118.7, 113.4, 93.8,
C
11H12NaO4 [MþNa]þ 231.0628, found: 231.0632.
77.5, 77.4, 77.2, 76.8, 68.5, 66.2, 61.2. HR-MS (ESI) calcd for
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

S. Yang et al. / Tetrahedron xxx (xxxx) xxx
7
C12H11NNaO3 [MþNa]þ 228.0631, found: 228.0632.
4.5.21. (2-((1,4-Dioxan-2-yl)oxy)phenyl)(pyrrolidin-1-yl)
methanone (3sa)
(101 mg, 73%) as a yellow oil, Hex/EA as the eluent (Hex/
4.5.15. 2-(4-(Trifluoromethyl)phenoxy)-1,4-dioxane (3ma)
EA ¼ 5:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.22 (t, J ¼ 6.9 Hz, 2H),
(99 mg, 80%) as a white solid, Hex/EA as the eluent (Hex/
7.09 (d, J ¼ 8.2 Hz, 1H), 6.99 (t, J ¼ 7.3 Hz, 1H), 5.16 (s, 1H), 4.05 (dd,
J ¼ 11.8, 5.7 Hz, 1H), 3.69 (d, J ¼ 12.1 Hz, 4H), 3.55 (t, J ¼ 6.7 Hz, 4H),
3.26 (s, 1H), 3.15 (dd, J ¼ 10.8, 5.3 Hz, 1H), 1.91e1.76 (m, 4H). 13C
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 12.60e12.51 (m, 1H),
7.55 (d, J ¼ 8.6 Hz, 2H), 7.15 (d, J ¼ 8.6 Hz, 2H), 5.33 (s, 1H), 4.10 (dq,
J ¼ 12.7, 6.4 Hz,1H), 3.93e3.83 (m, 2H), 3.79 (dd, J ¼ 8.3, 5.3 Hz, 2H),
NMR (101 MHz, CDCl3) d 167.7, 152.8,130.6,129.4,128.1, 123.1, 116.9,
3.60 (dt, J ¼ 11.8, 2.9 Hz, 1H). 13C NMR (101 MHz, CDCl3)
d 159.7,
95.2, 77.8, 77.7, 77.5, 77.2, 68.9, 66.3, 61.8, 48.1, 45.8, 26.2, 24.9. HR-
127.4, 127.4, 127.3, 127.3, 126.2, 125.2, 124.9, 124.6, 124.3, 123.5,
MS (ESI) calcd for
300.1208.
C
15H19NNaO4 [MþNa]þ 300.1206, found:
120.8, 116.9, 94.0, 77.8, 77.5, 77.2, 69.0, 66.6, 61.6. 19F NMR
(376 MHz, CDCl3)
d
ꢀ61.73. HR-MS (ESI) calcd for C11H11F3NaO3
[MþNa]þ 271.0552, found: 271.0551.
4.5.22. 2-(4-(Trifluoromethoxy)phenoxy)-1,4-dioxane (3ta)
(70 mg, 53%) as a yellow liquid, Hex/EA as the eluent (Hex/
4.5.16. 2-(2-(Trifluoromethyl)phenoxy)-1,4-dioxane (3na)
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.15 (d, J ¼ 8.9 Hz, 2H),
(115 mg, 93%) as a colorless liquid, Hex/EA as the eluent (Hex/
7.08 (d, J ¼ 8.9 Hz, 2H), 5.25 (s, 1H), 4.12 (dt, J ¼ 12.0, 6.0 Hz, 1H),
EA ¼ 10:1, v/v). 1H NMR (500 MHz, CDCl3)
d
7.50 (d, J ¼ 7.7 Hz, 1H),
3.87 (s, 2H), 3.82e3.77 (m, 2H), 3.60 (d, J ¼ 11.9 Hz, 1H). 13C NMR
7.40 (dd, J ¼ 11.6, 4.2 Hz, 1H), 7.21e7.17 (m, 1H), 7.00 (t, J ¼ 7.6 Hz,
1H), 5.21 (t, J ¼ 2.4 Hz, 1H), 4.07 (ddd, J ¼ 11.8, 6.5, 5.2 Hz, 1H), 3.80
(qd, J ¼ 11.9, 2.4 Hz, 2H), 3.73e3.68 (m, 2H), 3.54 (dt, J ¼ 11.7, 3.1 Hz,
(101 MHz, CDCl3) d 155.3, 143.9, 122.5, 121.9, 119.4, 117.5, 94.0, 77.5,
77.2, 76.8, 68.8, 66.3, 61.3. 19F NMR (376 MHz, CDCl3)
d
ꢀ58.37. HR-
MS (ESI) calcd for
287.0505.
C
11H11F3NaO4 [MþNa]þ 287.0502, found:
1H). 13C NMR (126 MHz, CDCl3)
d 154.9, 133.3, 127.1, 127.1, 127.1,
127.0, 124.8, 122.6, 121.7, 120.2, 120.0, 116.3, 94.4, 77.4, 77.2, 76.9,
68.4, 66.1, 61.5. 19F NMR (376 MHz, CDCl3)
d
ꢀ62.07. HR-MS (ESI)
4.5.23. 2-(4-Fluorophenoxy)-1,4-dioxane (3ua)
calcd for C11H11F3NaO3 [MþNa]þ 271.0552, found: 271.0551.
(10 mg, 10%) as a white solid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 7.06e6.94 (m, 4H), 5.19
(s, 1H), 4.13 (dt, J ¼ 11.8, 5.8 Hz, 1H), 3.89e3.81 (m, 2H), 3.77 (dd,
4.5.17. 2-(3-(Trifluoromethyl)phenoxy)-1,4-dioxane (3oa)
J ¼ 9.5, 6.0 Hz, 2H), 3.60 (dt, J ¼ 11.8, 3.2 Hz, 1H). 13C NMR (101 MHz,
(72 mg, 58%) as a colorless liquid, Hex/EA as the eluent (Hex/
CDCl3) d 156.9, 130.5, 125.9, 121.6, 119.7, 118.7, 113.4, 93.8, 77.5, 77.2,
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.40 (t, J ¼ 7.9 Hz, 1H),
76.8, 68.5, 66.2, 61.2. 19F NMR (376 MHz, CDCl3)
d
ꢀ122.05.
7.34 (s, 1H), 7.26 (t, J ¼ 6.6 Hz, 2H), 5.32 (s, 1H), 4.12 (dt, J ¼ 12.0,
6.1 Hz, 1H), 3.88 (s, 2H), 3.84e3.77 (m, 2H), 3.61 (dt, J ¼ 11.6, 2.6 Hz,
4.5.24. 1-(4-((1,4-Dioxan-2-yl)oxy)phenyl)propan-1-one (3va)
1H). 13C NMR (101 MHz, CDCl3)
d 156.6, 131.9, 131.6, 129.8, 125.0,
(91 mg, 77%) as a white solid, Hex/EA as the eluent (Hex/
122.3, 119.6, 118.6, 118.6, 113.3, 113.2, 93.5, 93.5, 77.2, 76.8, 76.5,
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.92 (d, J ¼ 8.4 Hz, 2H),
d
68.4, 65.9, 60.9. 19F NMR (376 MHz, CDCl3)
d
ꢀ62.73. HR-MS (ESI)
7.09 (d, J ¼ 8.4 Hz, 2H), 5.35 (s, 1H), 4.07 (dd, J ¼ 11.7, 6.1 Hz, 1H),
3.86 (s, 2H), 3.77 (d, J ¼ 2.5 Hz, 2H), 3.58 (d, J ¼ 11.7 Hz, 1H), 2.92 (q,
J ¼ 7.1 Hz, 2H), 1.18 (t, J ¼ 7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3)
calcd for C11H11F3NaO3 [MþNa]þ 271.0552, found: 271.0558.
4.5.18. 2-(4-(Methylsulfonyl)phenoxy)-1,4-dioxane (3pa)
d 199.5,160.4,131.2,130.1,116.0, 93.3, 77.5, 77.2, 76.8, 68.5, 66.1, 61.1,
(39 mg, 30%) as a yellow solid, Hex/EA as the eluent (Hex/
31.5, 8.4. HR-MS (ESI) calcd for C13H16NaO4 [MþNa]þ 259.0941,
EA ¼ 5:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.85 (d, J ¼ 8.7 Hz, 2H),
found: 259.0939.
7.20 (d, J ¼ 8.7 Hz, 2H), 5.37 (s, 1H), 4.10e4.03 (m, 1H), 3.88 (dd,
J ¼ 4.9, 1.6 Hz, 2H), 3.81e3.78 (m, 2H), 3.59 (d, J ¼ 11.8 Hz, 1H), 3.01
4.5.25. Ethyl 4-((1,4-dioxan-2-yl)oxy)benzoate (3wa)
(s, 3H). 13C NMR (101 MHz, CDCl3)
d
160.8, 133.7, 129.5, 116.8, 93.4,
(95 mg, 75%) as a yellow liquid, Hex/EA as the eluent (Hex/
77.5, 77.2, 76.8, 68.4, 66.1, 44.8. HR-MS (ESI) calcd for C11H14NaO5S
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.94 (d, J ¼ 8.4 Hz, 2H),
d
[MþNa]þ 281.0454, found: 281.0451.
7.04 (d, J ¼ 8.5 Hz, 2H), 5.30 (s, 1H), 4.29 (q, J ¼ 7.1 Hz, 2H), 4.04 (s,
1H), 3.82 (s, 2H), 3.76e3.70 (m, 2H), 3.54 (d, J ¼ 11.8 Hz, 1H), 1.32 (t,
J ¼ 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3)
d 165.8,160.0,131.1, 123.8,
115.5, 92.9, 92.9, 77.2, 76.8, 76.5, 68.1, 65.7, 60.7, 60.3, 14.0. HR-MS
4.5.19. 2-((1,4-Dioxan-2-yl)oxy)benzamide (3qa)
(61 mg, 55%) as a colorless solid, Hex/EA as the eluent (Hex/
(ESI) calcd for C13H16NaO5 [MþNa]þ 275.0890, found: 275.0895.
EA ¼ 2:1, v/v). 1H NMR (500 MHz, CDCl3)
d 8.26e8.20 (m, 1H), 7.99
(s, 1H), 7.47e7.42 (m, 1H), 7.18e7.10 (m, 2H), 6.09 (s, 1H), 5.54 (s,
1H), 4.11e4.05 (m, 1H), 3.99e3.88 (m, 2H), 3.85e3.81 (m, 2H), 3.57
4.5.26. 3-((1,4-dioxan-2-yl)oxy)pyridine (3ba)
(34 mg, 38%) as a yellow liquid, Hex/EA as the eluent (Hex/
(dd, J ¼ 11.9, 2.1 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 166.8, 154.2,
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 8.46 (s, 1H), 8.27 (s, 1H),
7.47e7.32 (m, 1H), 7.22 (dd, J ¼ 8.2, 4.5 Hz, 1H), 5.29 (s, 1H), 4.11 (dt,
133.1, 132.5, 122.3, 121.5, 114.5, 93.0, 77.2, 76.9, 76.7, 68.5, 66.2, 60.6.
HR-MS (ESI) calcd for C11H13F3NNaO4 [MþNa]þ 246.0737, found:
246.0738.
J ¼ 12.1, 6.2 Hz, 1H), 3.92e3.83 (m, 2H), 3.79 (dt, J ¼ 9.1, 4.5 Hz, 2H),
3.59 (dt, J ¼ 11.8, 2.8 Hz, 1H). 13C NMR (101 MHz, CDCl3)
d 153.13,
143.49, 139.70, 124.00, 123.48, 93.89, 77.48, 77.36, 77.16, 76.84,
68.60, 66.22, 61.18. HR-MS (ESI) calcd for C9H12NO3 [MþH]þ
182.0812, found: 182.0817.
4.5.20. 2-((1,4-Dioxan-2-yl)oxy)-N,N-diethylbenzamide (3ra)
(68 mg, 49%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 5:1, v/v). 1H NMR (400 MHz, CDCl3)
d
7.22 (d, J ¼ 4.3 Hz, 1H),
7.15 (d, J ¼ 7.2 Hz, 2H), 6.99 (s, 1H), 5.11 (s, 1H), 4.05 (s, 1H),
4.5.27. Methyl 4-((1,4-dioxan-2-yl)oxy)-3-methoxybenzoate (3a0a)
3.76e3.72 (m, 2H), 3.67 (d, J ¼ 3.9 Hz, 2H), 3.12 (s, 1H), 1.17 (t,
(122 mg, 91%) as a brown solid, Hex/EA as the eluent (Hex/
J ¼ 7.0 Hz, 6H),1.00 (s, 4H). 13C NMR (101 MHz, CDCl3)
d
168.4,152.8,
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.58 (dd, J ¼ 8.4, 1.5 Hz,
d
129.9,128.7,127.4, 122.9,117.0, 114.9, 95.6, 77.5, 77.4, 77.2, 76.8, 68.7,
66.0, 61.7, 42.9, 38.8, 14.0, 12.7. HR-MS (ESI) calcd for C15H21NNaO4
[MþNa]þ 302.1363, found: 302.1366.
1H), 7.53 (d, J ¼ 1.3 Hz, 1H), 7.11 (d, J ¼ 8.4 Hz, 1H), 5.30 (s, 1H), 4.13
(ddd, J ¼ 11.8, 7.2, 4.8 Hz,1H), 3.94e3.80 (m, 9H), 3.78e3.72 (m, 2H),
3.59e3.46 (m, 2H). 13C NMR (101 MHz, CDCl3)
d 166.7, 149.9, 149.8,
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

8
S. Yang et al. / Tetrahedron xxx (xxxx) xxx
124.6, 123.2, 116.4, 113.1, 94.4, 77.5, 77.2, 76.8, 74.9, 68.4, 66.6, 66.0,
61.3, 56.0, 52.0. HR-MS (ESI) calcd for C13H16NaO6 [MþNa]þ
291.0839, found: 291.0840.
64.1. HR-MS (ESI) calcd for C15H14NaO4 [MþNa]þ 281.0784, found:
281.0789.
4.5.34. 1-(1-((1,4-Dioxan-2-yl)oxy)naphthalen-2-yl)ethan-1-one
(3h0a)
4.5.28. 4-((1,4-Dioxan-2-yl)oxy)-3-methoxybenzonitrile (3b0a)
(95 mg, 81%) as a yellow solid, Hex/EA as the eluent (Hex/
(83 mg, 61%) as a yellow oil, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.20 (dd, J ¼ 8.4, 1.4 Hz,
d
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 8.26e8.20 (m, 1H), 7.84
1H), 7.14 (d, J ¼ 8.3 Hz, 1H), 7.09 (d, J ¼ 1.2 Hz, 1H), 5.30 (s, 1H),
4.14e4.06 (m, 1H), 3.92 (dd, J ¼ 12.0, 2.0 Hz, 1H), 3.84 (s, 3H),
3.78e3.74 (m, 2H), 3.60e3.52 (m, 2H). 13C NMR (101 MHz, CDCl3)
(d, J ¼ 5.7 Hz, 1H), 7.64 (q, J ¼ 8.6 Hz, 2H), 7.57 (dd, J ¼ 5.2, 2.7 Hz,
2H), 5.01 (d, J ¼ 5.6 Hz, 1H), 4.11 (d, J ¼ 11.6 Hz, 1H), 4.01 (d,
J ¼ 11.8 Hz,1H), 3.82 (dd, J ¼ 11.6, 5.8 Hz,1H), 3.70 (d, J ¼ 4.2 Hz, 2H),
3.58e3.51 (m, 1H), 2.74 (s, 3H). 13C NMR (101 MHz, CDCl3)
d 201.6,
d
150.6, 150.2, 126.3, 119.3, 117.4, 115.4, 106.2, 94.7, 77.8, 77.5, 77.2,
68.6, 66.3, 61.5, 56.5. HR-MS (ESI) calcd for C12H13NNaO4 [MþNa]þ
151.5, 136.5, 130.2, 128.2, 128.1, 128.1, 126.9, 125.1, 124.9, 123.4, 99.8,
77.5, 77.2, 76.8, 68.7, 65.9, 63.9, 31.2. HR-MS (ESI) calcd for
258.0737, found: 258.0736.
C
16H16NaO4 [MþNa]þ 295.0941, found: 295.0940.
4.5.29. 2-((1,4-Dioxan-2-yl)oxy)-3-methylbenzaldehyde (3c0a) [7b]
(60 mg, 54%) as a white solid, Hex/EA as the eluent (Hex/
4.5.35. 2-((1,4-Dioxan-2-yl)oxy)-6-methoxybenzaldehyde (3i0a)
EA ¼ 10:1, v/v). 1H NMR (400 MHz, CDCl3)
d 10.37 (s, 1H), 7.69 (d,
(122 mg, 60%) as a yellow solid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
10.51 (d, J ¼ 6.9 Hz, 1H),
d
J ¼ 7.7 Hz, 1H), 7.44 (d, J ¼ 7.4 Hz, 1H), 7.17 (t, J ¼ 7.6 Hz, 1H),
4.89e4.86 (m, 1H), 4.03 (d, J ¼ 11.6 Hz, 2H), 3.77 (dd, J ¼ 11.5, 6.0 Hz,
1H), 3.70 (d, J ¼ 2.4 Hz, 2H), 3.63 (td, J ¼ 11.1, 5.6 Hz, 1H), 2.34 (s,
7.42e7.36 (m, 1H), 6.80e6.75 (m, 1H), 6.62 (d, J ¼ 8.4 Hz, 1H),
5.28e5.25 (m, 1H), 4.10 (dd, J ¼ 12.0, 5.6 Hz, 1H), 3.92e3.82 (m, 5H),
3.75 (dd, J ¼ 6.3, 3.2 Hz, 2H), 3.60e3.55 (m, 1H). 13C NMR (126 MHz,
3H). 13C NMR (101 MHz, CDCl3)
d 191.4, 191.3, 157.3, 137.4, 132.3,
130.4, 126.7, 125.1, 99.2, 77.5, 77.2, 76.8, 68.8, 65.9, 64.1, 16.5. HR-MS
CDCl3) d 189.5, 161.8, 159.8, 135.9, 116.1, 108.9, 105.9, 94.9, 77.7, 77.4,
(ESI) calcd for C12H14NaO4 [MþNa]þ 245.0784, found: 245.0779.
77.2, 68.6, 66.3, 66.3, 61.8, 56.4. HR-MS (ESI) calcd for C12H14NaO5
[MþNa]þ 261.0733, found: 261.0734.
4.5.30. 2-((1,4-Dioxan-2-yl)oxy)-5-methoxybenzaldehyde (3d0a)
(67 mg, 56%) as a yellow liquid, Hex/EA as the eluent (Hex/
4.5.36. 4-((1,4-Dioxan-2-yl)oxy)-3-chlorobenzaldehyde (3j0a)
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d 10.48 (s, 1H), 7.30 (d,
(45 mg, 37%) as a yellow liquid, Hex/EA as the eluent (Hex/
J ¼ 3.0 Hz, 1H), 7.16 (d, J ¼ 9.1 Hz, 1H), 7.09 (dd, J ¼ 9.1, 2.8 Hz, 1H),
5.26 (s, 1H), 4.10 (dt, J ¼ 11.7, 5.8 Hz, 1H), 3.88 (d, J ¼ 2.1 Hz, 2H),
3.79e3.75 (m, 5H), 3.61 (dt, J ¼ 11.7, 3.0 Hz, 1H). 13C NMR (101 MHz,
EA ¼ 10:1, v/v). 1H NMR (500 MHz, CDCl3)
d 9.87 (s,1H), 7.92 (s, 1H),
7.74 (d, J ¼ 8.5 Hz, 1H), 7.31 (d, J ¼ 8.5 Hz, 1H), 5.41 (s, 1H), 4.14e4.10
(m, 1H), 4.01 (d, J ¼ 12.1 Hz, 1H), 3.91 (d, J ¼ 12.1 Hz, 1H), 3.83 (d,
J ¼ 5.6 Hz, 2H), 3.62 (d, J ¼ 11.8 Hz, 1H). 13C NMR (126 MHz, CDCl3)
CDCl3)
d 189.5, 189.5, 154.9, 153.7, 126.4, 123.5, 117.8, 110.1, 94.8,
77.5, 77.2, 76.8, 68.5, 66.1, 61.7, 55.8. HR-MS (ESI) calcd for
d
189.9, 157.4, 131.7, 131.5, 130.1, 125.0, 116.2, 94.4, 77.4, 77.4, 77.2,
C
12H14NaO5 [MþNa]þ 261.0733, found: 261.0728.
76.9, 68.3, 66.1, 61.4. HR-MS (ESI) calcd for C11H11ClNaO4 [MþNa]þ
265.0238, found: 265.0242.
4.5.31. Methyl 2,4-bis((1,4-dioxan-2-yl)oxy)benzoate (3e0a)
(51 mg, 30%) as a brown solid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.80 (d, J ¼ 8.8 Hz, 1H),
d
4.5.37. 1-(4-((1,4-Dioxan-2-yl)oxy)-3-methylphenyl)ethan-1-one
(3k0a)
6.93 (s, 1H), 6.82e6.74 (m, 1H), 5.32 (d, J ¼ 6.6 Hz, 1H), 5.20 (d,
J ¼ 9.2 Hz, 1H), 4.20 (ddd, J ¼ 11.6, 6.9, 4.6 Hz, 1H), 4.09 (dt, J ¼ 12.2,
6.3 Hz, 1H), 3.94 (dd, J ¼ 11.8, 2.2 Hz, 1H), 3.90e3.81 (m, 6H),
3.80e3.74 (m, 4H), 3.59 (ddd, J ¼ 17.4, 11.8, 3.2 Hz, 2H). 13C NMR
(25 mg, 21%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
7.79 (d, J ¼ 10.7 Hz, 2H),
d
7.10 (d, J ¼ 8.4 Hz, 1H), 5.36 (s, 1H), 4.08 (s, 1H), 3.91 (s, 2H), 3.80 (t,
J ¼ 5.9 Hz, 2H), 3.63 (d, J ¼ 12.6 Hz, 1H), 2.55 (s, 3H), 2.31 (s, 3H). 13
C
(101 MHz, CDCl3)
d 165.9, 165.9, 160.9, 160.8, 158.4, 158.4, 133.3,
NMR (126 MHz, CDCl3) d 197.3,158.9,131.4,131.2,128.3,127.7,113.3,
115.6, 115.5, 109.8, 109.7, 107.2, 106.8, 95.7, 95.5, 93.4, 93.3, 77.5,
77.2, 76.8, 68.6, 66.2, 66.1, 61.7, 61.6, 61.1, 51.9, 51.9. HR-MS (ESI)
calcd for C16H20NaO8 [MþNa]þ 363.1050, found: 363.1049.
93.4, 77.4, 77.2, 76.9, 68.8, 66.2, 61.6, 26.5, 16.5. HR-MS (ESI) calcd
for C13H16NaO4 [MþNa]þ 259.0941, found: 259.0949.
4.5.38. 1-(4-((1,4-Dioxan-2-yl)oxy)-2-methylphenyl)ethan-1-one
(3l0a)
4.5.32. 1-(2-((1,4-Dioxan-2-yl)oxy)-5-chlorophenyl)ethan-1-one
(3f0a)
(52 mg, 44%) as a brown liquid, Hex/EA as the eluent (Hex/
(51 mg, 40%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 5:1, v/v). 1H NMR (500 MHz, CDCl3)
d
7.74 (d, J ¼ 8.3 Hz, 1H),
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
7.65 (d, J ¼ 2.6 Hz, 1H),
d
6.94 (d, J ¼ 7.7 Hz, 2H), 5.36 (s, 1H), 4.10 (dt, J ¼ 12.1, 6.1 Hz, 1H),
3.95e3.84 (m, 2H), 3.80 (d, J ¼ 4.6 Hz, 2H), 3.60 (d, J ¼ 11.8 Hz, 1H),
7.33 (dd, J ¼ 8.9, 2.7 Hz, 1H), 7.11 (d, J ¼ 8.9 Hz, 1H), 5.33 (s, 1H),
4.09e3.97 (m, 1H), 3.87 (s, 2H), 3.77 (dd, J ¼ 4.8, 2.6 Hz, 2H), 3.58
(dt, J ¼ 11.7, 2.5 Hz, 1H), 2.64 (s, 3H). 13C NMR (101 MHz, CDCl3)
2.55 (s, 6H). 13C NMR (126 MHz, CDCl3)
d 199.9, 159.0, 142.2, 132.4,
131.3, 119.7, 113.0, 93.2, 77.4, 77.2, 76.9, 68.7, 66.3, 61.2, 29.3, 22.6.
HR-MS (ESI) calcd for C13H16NaO4 [MþNa]þ 259.0941, found:
259.0948.
d
198.5, 154.6, 133.4, 130.5, 130.3, 127.6, 117.0, 94.2, 94.1, 77.8, 77.5,
77.2, 68.8, 66.4, 61.6, 32.3, 32.3. HR-MS (ESI) calcd for C12H13ClNaO4
[MþNa]þ 279.0395, found: 279.0402.
4.5.33. 1-((1,4-Dioxan-2-yl)oxy)-2-naphthaldehyde (3g0a) [7b]
4.5.39. 4-((1,4-Dioxan-2-yl)oxy)-2-chlorobenzonitrile (3m0a)
(128 mg, 99%) as a yellow solid, Hex/EA as the eluent (Hex/
(56 mg, 47%) as a brown liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (400 MHz, CDCl3)
d
10.59 (s, 1H), 8.20 (d,
EA ¼ 10:1, v/v). 1H NMR (500 MHz, CDCl3)
7.58 (d, J ¼ 8.7 Hz, 1H),
d
J ¼ 8.2 Hz, 1H), 7.90e7.84 (m, 2H), 7.69 (d, J ¼ 8.6 Hz, 1H), 7.66e7.56
(m, 2H), 5.09 (d, J ¼ 5.6 Hz, 1H), 4.14 (t, J ¼ 13.9 Hz, 2H), 3.92 (dd,
7.22 (s, 1H), 7.05 (d, J ¼ 8.7 Hz, 1H), 5.33 (s, 1H), 4.05 (dq, J ¼ 13.0,
6.5 Hz, 1H), 3.88 (q, J ¼ 12.2 Hz, 2H), 3.81 (d, J ¼ 6.2 Hz, 2H), 3.60 (d,
J ¼ 11.7, 5.8 Hz, 1H), 3.75 (s, 2H), 3.66 (dd, J ¼ 16.4, 7.3 Hz, 1H). 13
C
J ¼ 11.8 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 160.3, 138.1, 134.9,
117.7, 116.1, 115.4, 106.1, 93.4, 77.2, 76.9, 76.7, 68.0, 65.9, 60.8. HR-MS
NMR (101 MHz, CDCl3)
d
190.9, 157.5, 138.0, 129.3, 128.5, 128.0,
127.1, 126.4, 125.4, 123.4, 122.8, 100.1, 77.5, 77.2, 76.8, 68.6, 65.9,
(ESI) calcd for C11H10ClNNaO3 [MþNa]þ 262.0241, found: 262.0244.
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

S. Yang et al. / Tetrahedron xxx (xxxx) xxx
9
4.5.40. 4-((1,4-Dioxan-2-yl)oxy)-3-(trifluoromethyl)benzonitrile
(3n0a)
(126 MHz, CDCl3)
d
165.9, 160.3, 130.4, 122.0, 114.6, 86.8, 76.3, 76.0,
75.8, 74.8, 50.8, 27.5. HR-MS (ESI) calcd for C13H18NaO4 [MþNa]þ
(85 mg, 62%) as a brown liquid, Hex/EA as the eluent (Hex/
261.1097, found: 261.1105.
EA ¼ 10:1, v/v). 1H NMR (500 MHz, CDCl3)
d 7.88 (s, 1H), 7.78 (d,
J ¼ 8.7 Hz, 1H), 7.36 (d, J ¼ 8.7 Hz, 1H), 5.41 (s, 1H), 4.13e4.01 (m,
1H), 3.91 (dd, J ¼ 36.9,12.2 Hz, 2H), 3.80 (d, J ¼ 20.3 Hz, 2H), 3.61 (d,
4.5.47. Methyl 4-(1-ethoxyethoxy)benzoate (3af)
(26 mg, 23%) as a yellow liquid, Hex/EA as the eluent (Hex/
J ¼ 11.7 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 158.0, 137.4, 131.5,
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
7.97 (d, J ¼ 8.8 Hz, 2H),
d
131.4, 125.7, 123.5, 121.4, 121.3, 121.2, 120.9, 120.7, 119.1, 117.8, 116.5,
7.01 (d, J ¼ 8.8 Hz, 2H), 5.48 (q, J ¼ 5.3 Hz, 1H), 3.89 (s, 3H), 3.76 (dq,
J ¼ 14.2, 7.1 Hz, 1H), 3.54 (dq, J ¼ 14.3, 7.1 Hz, 1H), 1.53 (d, J ¼ 5.3 Hz,
105.3, 94.1, 77.4, 77.4, 77.2, 76.9, 68.0, 65.9, 61.3. 19F NMR (471 MHz,
ꢀ63.11. HR-MS (ESI) calcd for C12H10F3NNaO3 [MþNa]þ
3H), 1.20 (t, J ¼ 7.1 Hz, 3H). 13C NMR (126 MHz, CDCl3)
d
167.0, 161.0,
CDCl3)
d
296.0505, found: 296.0508.
131.7, 116.5, 99.3, 77.4, 77.2, 76.9, 61.4, 52.0, 20.2, 15.3. HR-MS (ESI)
calcd for C12H16NaO4 [MþNa]þ 247.0941, found: 247.0934.
4.5.41. 4-((1,4-Dioxan-2-yl)oxy)-3,5-dimethylbenzonitrile (3o0a)
(51 mg, 44%) as a white solid, Hex/EA as the eluent (Hex/
4.5.48. The mixture of methyl 4-(1,2-dimethoxyethoxy)benzoate
(3 ag) and methyl 4-((2-methoxyethoxy)methoxy)benzoate (3 ag0)
(30 mg, 30%) as a brown liquid, Hex/EA as the eluent (Hex/
EA ¼ 10:1, v/v). 1H NMR (500 MHz, CDCl3)
d 7.32 (s, 2H), 4.92e4.85
(m, 1H), 4.12 (dd, J ¼ 10.2, 5.3 Hz, 1H), 3.94 (d, J ¼ 11.6 Hz, 1H), 3.77
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
7.91 (dd, J ¼ 8.8, 3.5 Hz,
d
(dd, J ¼ 11.7, 5.1 Hz, 1H), 3.73 (t, J ¼ 4.2 Hz, 2H), 3.69e3.60 (m, 1H),
2.31 (s, 6H). 13C NMR (126 MHz, CDCl3)
d 157.6, 132.8, 132.7, 118.7,
3H), 6.99 (d, J ¼ 8.7 Hz, 3H), 5.30 (t, J ¼ 5.1 Hz, 1H), 5.24 (s, 1H), 3.81
(d, J ¼ 1.3 Hz, 5H), 3.77e3.73 (m, 1H), 3.61 (dd, J ¼ 10.6, 5.4 Hz, 1H),
3.54 (dd, J ¼ 10.6, 4.8 Hz, 1H), 3.49e3.45 (m, 1H), 3.36 (s, 6H), 3.29
(s, 2H). HR-MS (ESI) calcd for C12H16NaO5 [MþNa]þ 263.0890,
found: 263.0891.
107.8, 98.3, 77.2, 76.9, 76.7, 68.6, 65.7, 63.2, 17.0. HR-MS (ESI) calcd
for C13H15NNaO3 [MþNa]þ 256.0944, found: 256.0947.
4.5.42. Methyl 4-((1,4-dioxan-2-yl)oxy)-3-bromobenzoate (3p0a)
(32 mg, 20%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
d 8.25 (s, 1H), 7.94 (d,
J ¼ 8.7 Hz,1H), 7.18 (d, J ¼ 8.6 Hz,1H), 5.37 (s,1H), 4.18e4.11 (m,1H),
4.5.49. Methyl 4-((1,3-dioxan-4-yl)oxy)benzoate (3ah)
(10 mg, 8%) as a yellow liquid, Hex/EA as the eluent (Hex/
3.99 (t, J ¼ 13.8 Hz, 1H), 3.91 (d, J ¼ 9.7 Hz, 4H), 3.86e3.77 (m, 2H),
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
d 8.03e7.96 (m, 2H),
7.11e7.05 (m, 2H), 5.67 (t, J ¼ 3.1 Hz,1H), 5.13 (d, J ¼ 6.3 Hz,1H), 4.78
3.61 (d, J ¼ 11.8 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 165.5, 156.9,
134.9, 130.2, 125.0, 115.3, 112.7, 94.2, 77.2, 76.9, 76.7, 68.2, 65.9, 61.2,
52.1. HR-MS (ESI) calcd for C12H13BrNaO5 [MþNa]þ 338.9839,
found: 338.9848.
(d, J ¼ 6.3 Hz, 1H), 4.21 (dd, J ¼ 11.2, 3.0 Hz, 1H), 4.02e3.95 (m, 1H),
3.89 (s, 3H), 2.39e2.29 (m, 1H), 1.87 (dq, J ¼ 13.7, 3.0 Hz, 1H). 13
C
NMR (126 MHz, CDCl3)
d 166.9, 160.4, 131.7, 124.1, 116.1, 94.3, 87.9,
77.4, 77.2, 76.9, 62.9, 52.1, 30.7. HR-MS (ESI) calcd for C12H14NaO5
4.5.43. Methyl 4-((tetrahydrofuran-2-yl)oxy)benzoate (3 ab)
[MþNa]þ 261.0733, found: 261.0731.
(101 mg, 91%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
7.94 (dd, J ¼ 8.8, 1.8 Hz,
d
4.5.50. Methyl 4-((tetrahydrothiophen-2-yl)oxy)benzoate (3ai)
2H), 7.01 (dd, J ¼ 8.8, 1.8 Hz, 2H), 5.82 (d, J ¼ 3.4 Hz, 1H), 4.03e3.97
(m, 1H), 3.92 (dt, J ¼ 7.6, 4.1 Hz, 1H), 3.84 (d, J ¼ 2.1 Hz, 3H),
2.21e2.05 (m, 3H), 1.99e1.87 (m, 1H). 13C NMR (126 MHz, CDCl3)
(12 mg, 10%) as a yellow liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
7.99 (dd, J ¼ 6.7, 4.8 Hz,
d
2H), 6.87 (t, J ¼ 5.8 Hz, 2H), 5.92 (dd, J ¼ 4.8, 1.3 Hz, 1H), 3.88 (s, 3H),
3.06 (ddd, J ¼ 10.0, 6.5, 3.3 Hz, 1H), 2.91 (td, J ¼ 10.0, 6.8 Hz, 1H),
2.49 (d, J ¼ 13.1 Hz, 1H), 2.28e2.18 (m, 2H), 2.06 (tdd, J ¼ 11.8, 6.8,
d
167.1, 161.3, 131.7, 123.4, 116.1, 102.4, 77.7, 77.4, 77.2, 68.6, 52.1,
33.0, 23.7, 23.6. HR-MS (ESI) calcd for C12H14NaO4 [MþNa]þ
245.0784, found: 245.0789.
4.9 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 166.7, 160.4, 131.4, 123.0,
115.1, 86.3, 77.2, 76.9, 76.7, 51.8, 38.2, 32.6, 28.3. HR-MS (ESI) calcd
4.5.44. Methyl 4-((1,3-dioxolan-4-yl)oxy)benzoate (3ac)
for C12H14NaO3S [MþNa]þ 261.0556, found: 261.0559.
(25 mg, 22%) as a brown liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v).1H NMR (500 MHz, CDCl3)
d 8.04e7.92 (m, 2H), 7.05
(d, J ¼ 8.2 Hz, 2H), 5.48 (s, 1H), 3.93e3.78 (m, 4H), 3.64e3.56 (m,
4.5.51. Methyl 4-((dimethylcarbamoyl)oxy)benzoate (3aj) [25]
(64 mg, 57%) as a white solid, Hex/EA as the eluent (Hex/
1H), 1.99 (dt, J ¼ 16.7, 7.8 Hz, 1H), 1.89e1.83 (m, 2H), 1.74e1.63 (m,
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
8.03 (d, J ¼ 8.7 Hz, 2H),
d
2H), 1.59 (dd, J ¼ 9.0, 4.2 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d 167.0,
7.18 (d, J ¼ 8.7 Hz, 2H), 3.88 (s, 3H), 3.08 (s, 3H), 3.00 (s, 3H). 13C
161.0, 131.5, 123.3, 116.0, 96.2, 77.4, 77.2, 76.9, 62.1, 51.9, 30.2, 25.2,
18.6. HR-MS (ESI) calcd for C11H12NaO5 [MþNa]þ 247.0577, found:
247.0579.
NMR (126 MHz, CDCl3)
d 166.6, 155.3, 154.2, 131.1, 127.0, 121.6, 77.4,
77.2, 76.9, 52.2, 36.8, 36.6, 27.9. HR-MS (ESI) calcd for C11H13NNaO4
[MþNa]þ 246.0737, found: 261.0741.
4.5.45. Methyl 4-((tetrahydro-2H-pyran-2-yl)oxy)benzoate (3ad)
4.5.52. Methyl 4-(benzyloxy)benzoate (3ak)
(39 mg, 33%) as a brown liquid, Hex/EA as the eluent (Hex/
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
d 8.04e7.92 (m, 2H), 7.05
(d, J ¼ 8.2 Hz, 2H), 5.48 (s, 1H), 3.93e3.78 (m, 4H), 3.64e3.56 (m,
(6 mg, 5%) as a white solid, Hex/EA as the eluent (Hex/EA ¼ 20:1,
v/v). 1H NMR (500 MHz, CDCl3)
d
7.99 (d, J ¼ 8.8 Hz, 2H), 7.46e7.32
(m, 5H), 6.99 (d, J ¼ 8.8 Hz, 2H), 5.12 (s, 2H), 3.88 (s, 3H). 13C NMR
1H), 1.99 (dt, J ¼ 16.7, 7.8 Hz, 1H), 1.89e1.83 (m, 2H), 1.74e1.63 (m,
2H), 1.59 (dd, J ¼ 9.0, 4.2 Hz, 1H). 13C NMR (126 MHz, CDCl3)
d
167.0,
(126 MHz, CDCl3)
d 167.2, 162.9, 136.7, 132.0, 129.1, 128.6, 127.9,
123.3, 114.9, 77.7, 77.4, 77.2, 70.5, 52.3. HR-MS (ESI) calcd for
161.0, 131.5, 123.3, 116.0, 96.2, 77.4, 77.2, 76.9, 62.1, 51.9, 30.2, 25.2,
18.6. HR-MS (ESI) calcd for C13H16NaO4 [MþNa]þ 259.0941, found:
259.0943.
C
15H14NaO3 [MþNa]þ 265.0835, found: 265.0837.
Declaration of competing interest
4.5.46. Methyl 4-(tert-butoxymethoxy)benzoate (3ae)
(43 mg, 36%) as a yellow liquid, Hex/EA as the eluent (Hex/
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
EA ¼ 20:1, v/v). 1H NMR (500 MHz, CDCl3)
d 8.01e7.94 (m, 2H), 7.03
(d, J ¼ 8.9 Hz, 2H), 5.36 (s, 2H), 3.88 (s, 3H), 1.27 (s, 9H). 13C NMR
Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569

10
S. Yang et al. / Tetrahedron xxx (xxxx) xxx
(c) B.D. Barve, Y.-C. Wu, M. El-Shazly, M. Korinek, Y.-B. Cheng, J.-J. Wang, F.-
Acknowledgments
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Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2020.131569.
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Please cite this article as: S. Yang et al., Construction of CeO bond via cross-dehydrogenative coupling of sp [3] CeH bond with phenols catalyzed
by copper porphyrin, Tetrahedron, https://doi.org/10.1016/j.tet.2020.131569