Bu4NI-catalyzed α-acyloxylation reaction of ethers and ketones with aldehydes and tert-butyl hydroperoxide

Article abstract of DOI:10.1016/j.tet.2014.11.002

The reaction of (hetero)aromatic aldehydes or cinnamaldehyde with di-/multi-ethers in the presence of Bu₄NI and tert-butyl hydroperoxide generated corresponding α-acyloxy ethers. Reactions between (hetero)aromatic aldehydes or cyclohexanecarbaldehyde with arylalkyl ketones under similar conditions resulted in α-acyloxy ketones. Collectively, Bu₄NI-catalyzed α-acyloxylation reactions exhibit a broad scope of substrates and a high compatibility with functional groups.

Full text of DOI:10.1016/j.tet.2014.11.002

Accepted Manuscript
Bu NI-catalyzed α-acyloxylation reaction of ethers and ketones with aldehydes and
4
tert-butyl hydroperoxide
Feng Zhu , Zhong-Xia Wang
PII:
S0040-4020(14)01545-2
10.1016/j.tet.2014.11.002
TET 26150
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 August 2014
Revised Date: 30 October 2014
Accepted Date: 3 November 2014
Please cite this article as: Zhu F, Wang Z-X, Bu NI-catalyzed α-acyloxylation reaction of ethers
4
and ketones with aldehydes and tert-butyl hydroperoxide, Tetrahedron (2014), doi: 10.1016/
j.tet.2014.11.002.
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ACCEPTED MANUSCRIPT
Graphical abstract
1

ACCEPTED MANUSCRIPT
Bu NI-catalyzed α-acyloxylation reaction of ethers and ketones
4
with aldehydes and tert-butyl hydroperoxide
Feng Zhu, Zhong-Xia Wang*
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui
2
30026, People’s Republic of China
Tel: 86 551 63603043; Fax: 86 551 63601592
*
Corresponding author. E-mail: zxwang@ustc.edu.cn
Abstract
The reaction of (hetero)aromatic aldehydes or cinnamaldehyde with di-/multi-ethers in the
presence of Bu NI and tert-butyl hydroperoxide generated corresponding α-acyloxy ethers.
4
Reactions between (hetero)aromatic aldehydes or cyclohexanecarbaldehyde with arylalkyl
ketones under similar conditions resulted in α-acyloxy ketones. Collectively,
Bu NI-catalyzed α-acyloxylation reactions exhibit a broad scope of substrates and a high
4
compatibility with functional groups.
Keywords: α-acyloxylation ethers, ketones, TBHP oxidation, iodide catalysis
,
1
. Introduction
α-Acyloxy ethers and α-acyloxy ketones are significant intermediates or building blocks in
1
,2
synthetic organic chemistry, and are the structural units of important biological and
3
medicinal molecules. α-Acyloxy ethers can be prepared by the substitution reaction of
4
5
carboxylic salts to α-halo ethers, the esterification of hemiacetals, the addition of carboxylic
6
7
acids to alkenyl ethers, or the reductive acylation of esters. α-Acyloxy ketones can be
8
prepared by the substitution reaction of α-halo ketones with carboxylic salts, the direct
oxidative coupling of carbonyl compounds with heavy metal oxidants [such as Pb(OAc)4,
9
Tl(OAc) and Mn(OAc) ], the Cu-catalyzed insertion reaction of α-diazo ketones with
3
3
1
0
carboxylic acids, or the conjugate addition of acyloxy groups to alkynylphenyliodonium
11
salts. Recently, some new methodologies have been developed to improve reaction
efficiency and employ environmentally benign chemicals. For example, α-acyloxy ketones
have been synthesized through the α-acyloxylation of ketones by hypervalent
1
2
13
organoiodanes, gold-catalyzed hydration of propargyl acetates, or Bu NI-catalyzed
4
2

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coupling of carboxylic acids and ketones in the presence of tert-butyl hydroperoxide (TBHP)
1
4
or hydrogen peroxide. α-Acyloxy ethers were synthesized through CuO nanoparticle- or
Bu NI-catalyzed cross-dehydrogenative coupling reaction of carboxylic acids with ethers
4
1
5
using TBHP as the oxidant. Among the methods, Bu NI-catalyzed oxidative coupling of
4
carboxylic acids and ethers or ketones using TBHP or hydrogen peroxide as the oxidant is
attractive because (1) the reactions are transition metal-free; (2) TBHP and hydrogen
peroxide are environmentally benign oxidants; and (3) the reactions via C-H cleavage are
atom economical. In fact, the combination of tetrabutylammonium iodide and TBHP is a
versatile oxidizing system and has promoted a series of oxidative transformations of organic
1
6
substrates. Further examples of α-acyloxylation using this oxidizing system include
3
oxidative esterification of sp C-H bonds (adjacent to an oxygen atom) of cyclic ethers and
−
17
esters using terminal aryl alkenes and alkynes as the ArCOO sources and benzylic
acyloxylation of alkylarenes using aromatic aldehydes, alcohols, carboxylic acids or
1
8
toluenes. Inspired by these achievements, we developed the Bu NI/TBHP oxidation
4
methodology of ketones and ethers using aldehydes as coupling partners, which provides an
alternative and atom-economical method for the synthesis of α-acyloxy ethers and α-acyloxy
ketones. This approach extends the substrate scope of α-acyloxylation reaction of ethers and
ketones. Herein we report the results.
2
. Results and discussion
We first investigated the reaction between aldehydes and ethers. The reaction of
-bromobenzaldehyde with 1,4-dioxane was used for condition screening (Table 1). In the
presence of 6 equiv. of TBHP (70% aqueous solution), Bu NI catalyzed the reaction at
4
4
1
00 °C, giving 1,4-dioxan-2-yl 4-bromobenzoate at 56% yield. KI resulted in 21% yield
under the same conditions. Both Bu NCl and Bu NBr were catalytically ineffective. Hence it
4
4
seems that the iodide anion is crucial for the catalysis. In the absence of catalysts the reaction
could not occur. Proper oxidant is also crucial for the occurrence of the reaction. No desired
product was observed in the absence of oxidant. Additionally, no product was observed using
oxoane, benzoquinone or H O as the oxidants (Table 1, entries 6-9). A decane solution of
2
2
TBHP was more effective than the aqueous solution, the former leading to 70% yield (Table 1,
entry 10). Product yield was maximized at ~100 °C (Table 1, entries 10-12). Less TBHP (4
equiv.) resulted in decreased yield while higher loading of TBHP (8 equiv.) gave higher
product yield (Table 1, entries 10,13, and 14). Furthermore, lower catalyst loading resulted in
3

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a lower yield, whereas higher loadings of Bu NI gave similar result to that of 20 mol%
4
loadings (Table 1, entries 14, 15, and 16). Finally, the reaction in air resulted in lower yield as
compared to the identical reaction under N (Table 1, entries 10 and 17).
2
a
Table 1. Screening of reaction conditions
b
Entry
Cat. (mol%)
Oxidant (equiv.) Temp. (°C) Yield (%)
c
1
Bu NI (20)
TBHP (6)
TBHP (6)
TBHP (6)
TBHP (6)
TBHP (6)
100
100
100
100
100
100
100
56
21
−
4
c
2
KI (20)
c
3
Bu NCl (20)
4
c
4
Bu NBr (20)
−
4
c
5
−
−
6
7
8
Bu NI (20)
−
−
4
Bu NI (20)
oxoane (6)
−
4
Bu NI (20)
benzoquinone (6) 100
−
4
9
Bu NI (20)
H O (6)
100
100
70
−
4
2
2
d
1
0
Bu NI (20)
TBHP (6)
TBHP (6)
TBHP (6)
TBHP (4)
TBHP (8)
TBHP (8)
TBHP (8)
TBHP (6)
70
65
60
60
78
72
78
66
4
d
11
Bu NI (20)
4
d
1
1
1
1
1
1
2
3
4
5
6
7
Bu NI (20)
120
100
100
100
100
100
4
d
Bu NI (20)
4
d
Bu NI (20)
4
d
Bu NI (10)
4
d
Bu NI (30)
4
d,e
Bu NI (20)
4
a
Unless otherwise specified, the reactions were carried out using 0.5 mmol of
b
c
4
-bromobenzaldehyde and 2 mL of dioxane under N for 16 h. Isolated yield. 70%
2
d
e
aqueous solution of TBHP was used. A 5.5 M solution of TBHP in decane was employed.
Reaction was run in air.
The scope of aldehydes was examined using the reaction with 1,4-dioxane under the
optimized conditions (Table 2). The reaction of both 1- and 2-naphthaldehyde resulted in
corresponding esters in 56% and 73% yields, respectively. Electron-rich and -poor substituted
benzaldehydes were suitable substrates, but electron-rich aromatic aldehydes gave higher
4

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yields (Table 2, entries 3-9). Para-chloro- and para-bromobenzaldehydes led to the highest
yields among the electron-rich and -poor benzaldehydes. A dialdehyde, terephthalaldehyde,
could also react with 1,4-dioxane in the presence of 40 mol% Bu NI and 8 equiv. of TBHP,
4
leading to di(1,4-dioxan-2-yl)terephthalate in 40% yield. The reaction of electron-rich
heteroaromatic aldehydes such as thiophene-2-carbaldehyde and furan-2-carbaldehyde gave
comparable results with the electron-rich benzaldehydes. Electron-poor heteroaromatic
aldehydes (picolinaldehyde and nicotinaldehyde) did not form any desired products. The
reaction of cinnamaldehyde with 1,4-dioxane was unexceptional, resulting in 1,4-dioxan-2-yl
cinnamate in 57% yield. However, the reaction of 2-phenylacetaldehyde with 1,4-dioxane led
to an unexpected result, generating 1,4-dioxan-2-yl benzoate in 51% yield. Further
examination revealed that other 2-arylacetaldehydes behaved similarly upon reaction with
1
,4-dioxane or 1,3-dioxolane (Table 2, entries 16-20). Patel et al. reported that, in the
presence of Bu NI, styrene was oxidized by TBHP into phenylglyoxal, which further loses
4
1
7
the CO in the presence of Bu NI/TBHP to form benzaldehyde. In our reaction system
4
2
-phenylacetaldehyde may been similarly transformed into benzaldehyde through
α-oxidation of 2-phenylacetaldehyde and the following release of CO in the presence of
Bu NI/TBHP. The benzaldehyde undergoes the same reaction with a cyclic ether as the other
4
aromatic aldehydes to afford an α-acyloxy ether. Other nonaromatic aldehydes including
3
-phenylpropanal and butyraldehyde were also examined for the transformation. Neither of
them can give desired products. 3-Phenylpropanal gave a small amount of tert-butyl
-phenylpropaneperoxoate and a mixture of unidentified species. Butyraldehyde led to a
3
mixture of unidentified components.
a
Table 2. Bu NI-catalyzed α-acyloxylation reaction of 1,4-dioxane with various aldehydes
4
b
Entry Aldehyde
1
Product
Yield (%)
56
2
73
5

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CHO
3
65
MeO
4
5
64
66
6
7
8
67
48
44
CHO
MeOOC
CHO
9
1
58
73
78
40
F
0
11
c
1
2
3
1
66
6

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1
4
5
61
1
57
1
6
7
51
68
1
O
O
O
O
Cl
1
8
73
1
9
0
80
53
d
2
a
Unless otherwise specified, the reactions were carried out on a 0.5 mmol scale according
to the conditions indicated by the above equation. 2 mL of dioxane was used as the reactant
b
c
and solvent. TBHP used in the reactions is a 5.5 M solution in decane. Isolated yield. 40
mol% of Bu NI was employed. d 1,3-Dioxolane was used to replace 1,4-dioxane.
4
Other cyclic and acyclic ethers were also tested for the reaction. Simple ethers such as THF,
diethyl ether and dibutyl ether could not perform the α-acyloxylation reaction with
4
1
-bromo-benzaldehyde. Reaction of 1,3-dioxolane with 4-bromobenzaldehyde resulted in
,3-dioxolan-4-yl 4-bromobenzoate in 56% yield. Reaction of dimethoxymethane selectively
occurred at the terminal methyl groups, forming (methoxymethoxy)methyl 4-bromobenzoate
in low yield. Reaction of 1,2-dimethoxyethane afforded two products, 1,2-dimethoxyethyl
4
-bromobenzoate and (2-methoxyethoxy)methyl 4-bromobenzoate in 40% and 23% yields,
respectively. Interestingly, the α-acyloxylation reaction of 1,4,7,10-tetraoxacyclododecane
with 4-bromo-benzaldehyde can be smoothly carried out, giving
,4,7,10-tetraoxacyclododecan-2-yl 4-bromobenzoate in 80% yield. This provides a useful
method for the functionalization of crown ethers.
1
7

ACCEPTED MANUSCRIPT
a
Table 3. α-Acyloxylation reaction of ethers with 4-bromobenzaldehyde
Entry
1
Ether
Product
Yield
b
(%)
56
2
3
O
O
26
40
+
2
3
c
4
O
O
80
O
O
a
Unless otherwise specified, the reactions were carried out on a 0.5 mmol scale according
to the conditions indicated by the above equation, 2 mL of ethers were used as the reactant
b
c
and solvent. TBHP used in the ewactions is a 5.5 M solution in decane. Isolated yield. 5
equiv. of 1,4,7,10-tetraoxacyclododecane and 2 mL of EtOAc were employed.
We found that the catalytic system used above also promoted the reaction of
3
3
-methoxybenzaldehyde (A) with propiophenone (B), producing 1-oxo-1-phenylpropan-2-yl
-methoxybenzoate in 60% yield (Table 4). Lowering TBHP loading to 4 equiv. did not
decrease the yield (Table 4, entries 1 and 2). The ratio of reactants was found to affect the
reaction efficiency markedly. A 2:1 ratio of A to B gave the highest product yield, while a 1:2
ratio of A to B resulted in a significant decrease in yield. When the ratio of A to B was 2:1,
increasing TBHP loadings from 4 equiv. to 6 equiv. also caused a slight yield decrease (Table
4
, entries 3 and 4). Thus, it seems that higher TBHP loadings are unfavourable for this
reaction.
8

ACCEPTED MANUSCRIPT
a
Table 4. Optimization of reaction conditions
b
Entry
TBHP
A : B
Yield (%)
(equiv.)
1
2
3
4
5
8
4
4
4
6
1:1
1:1
2:1
1:2
2:1
60
62
80
69
73
a
The reactions were carried out using 0.5 mmol A according to the conditions indicated by
the above equation. TBHP used in the reactions is a 5.5 M solution in decane; EtOAc (3 mL)
b
was used as solvent. Isolated yield.
Under the optimized conditions, propiophenone could react with a series of aldehydes
including various aromatic/heteroaromatic aldehydes and an aliphatic aldehyde (Scheme 1).
The yields range from 45% to 84%. Among the aldehydes, 2-naphthaldehyde gave the
highest yield (84%); thiophene-2-carbaldehyde resulted in a moderate yield (65%); whereas
aliphatic aldehyde, cyclohexanecarbaldehyde, led to relatively low yield (45%). The reaction
of 1-(4-methoxyphenyl)propan-1-one with 3-methoxybenzaldehyde resulted in lower product
yield than the reaction of propiophenone with 3-methoxybenzaldehyde (70% vs. 80%). The
reaction of 1-phenylbutan-1-one with 3-methoxybenzaldehyde resulted in a nearly identical
yield to that of propiophenone with 3-methoxybenzaldehyde (81% vs. 80%). The reaction of
a dialdehyde, terephthalaldehyde, with propiophenone was also carried out using 40 mol% of
Bu NI as the catalyst and
6
equiv. of TBHP as the oxidant, forming
4
bis(1-oxo-1-phenylpropan-2-yl) terephthalate in 47% yield (Scheme 2). In addition, we also
found that the reaction of a dialkyl ketone, 1-cyclohexylpropan-1-one, with a aromatic
aldehyde, 3-methoxybenzaldehyde, under the same conditions as shown in Scheme 1 cannot
lead to the desired product; rather, tert-butyl 3-methoxybenzoperoxoate and unreacted
1
-cyclohexylpropan-1-one were obtained.
9

ACCEPTED MANUSCRIPT
Scheme 1. Reaction of arylalkyl ketones with aldehydes. Reaction conditions: ketones (0.5
mmol), aldehydes (1 mmol), Bu NI (20 mol%), TBHP (4 equiv., 5.5 M solution in decane),
4
EtOAc (3 mL); 100 °C, 16 h.
Scheme 2. Reaction of terephthalaldehyde with propiophenone
At first glance it seems as if the oxidative dehydrogenative reaction of aldehydes and
ethers or ketones proceeded via carboxylic acids derived from oxidation of the aldehydes
because carboxylic acids have been demonstrated to couple with an ether or ketone under
14,15b
similar conditions.
However, it was reported that the reaction of aromatic aldehydes
(
ArCHO) with TBHP in the presence of Bu NI yielded ArC(O)OOtBu rather than aromatic
4
1
9
carboxylic acids. B. Wang et al. also indicated that TBHP/Bu NI combination cannot drive
4
18a
the conversion of PhCHO into PhCOOH. We confirmed that the reaction between an
aromatic aldehyde and THF or diethyl ether could not occur under present conditions,
1
0

ACCEPTED MANUSCRIPT
whereas reaction between an aromatic carboxylic acid and THF or diethyl ether could occur
1
5b
under similar conditions as reported in literature and by our test. Due to easy formation of
ArC(O)OOtBu through reaction of ArCHO and TBHP catalyzed by Bu NI, we infer that
4
ArC(O)OOtBu may be the intermediate in the process of our oxidative dehydrogenative
reactions. Indeed, we obtained 1,4-dioxan-2-yl benzoate and 1-oxo-1-phenylpropan-2-yl
benzoate, respectively, in good yields through reaction of PhC(O)OOtBu with 1,4-dioxane or
propiophenone at 100 °C in the presence of 20 mol% of Bu NI (Scheme 3). In the absence of
4
Bu NI heating the mixture of PhC(O)OOtBu and 1,4-dioxane did not form 1,4-dioxan-2-yl
4
benzoate. Hence, Bu NI is necessary in this step. In addition, Ishihara et al. indicated that in
4
the Bu NI/TBHP-promoted α-acyloxylation reaction of carbonyl compounds with carboxylic
4
+
−
+
−
acids ammonium hypoiodite ([Bu N] [IO] ) or iodite ([Bu N] [IO ] ) might be the active
4
4
2
1
4
species. However, Wan et al. indicated that the existence of ammonium hypoiodite halted
1
9
the aldehyde C-H oxidation to tert-butyl perester. Our test showed that ammonium
hypoiodite could not promote the transformation of tert-butyl perester to α-acyloxy ethers or
Scheme 3. Reaction of PhC(O)OOtBu with 1,4-dioxane or propiophenone
−
α-acyloxy ketones under our experimental conditions. It is possible that part of the I was
−
−
oxidized to [IO] or [IO ] , but our reactions seem to proceed via another pathway. On the
2
basis of the experimental facts and the literature results, we propose a mechanism for the
oxidative dehydrogenative reactions of aldehydes and ethers or ketones as shown in Scheme
4
. In this mechanism, formation of tert-butyl perester follows the routes as proposed
1
8a,19
previously.
Meanwhile, the tert-butoxyl and tert-butylperoxy radicals generated through
−
reaction of TBHP with the iodide anion (following TBHP with I /OH [step a]) extract α-H
2
11

ACCEPTED MANUSCRIPT
from an ether or aryl alkyl ketone, forming α-carbon radicals. The α-carbon radicals react
with tert-butyl perester to yield α-acyloxy ethers or α-acyloxy ketones and a tert-butoxyl
radical (steps b and c). In contrast with 1,4-dioxane, THF is inactive under the same
conditions. This may result from the reactivity difference of α-THF radical and 1,4-dioxanyl
2
0
radical.
a)
tBuOOH
tBuO + OH
I
I2 (+ IO or IO2
tBuOO + H O
tBuOOH + OH
2
O
O
b)
R
O
tBuO or tBuOO
tBu
O
O
O
R
O
O
H
O
O
O
tBuO
tBu
tBuOH or tBuOOH
O
O
c)
R
O
tBuO or tBuOO
O
O
O
O
R
R1
R1
tBuOH or tBuOOH
R1
O
tBuO
Scheme 4. A proposed mechanism
We cannot rule out the mechanism as shown in Scheme 5. In this mechanism, tert-butyl
perester is also the key intermediate. It reacts with iodide anion to form a tert-butoxyl radical,
–
–
carboxylate anion, and I /IO /IO . The tert-butoxyl radical extracts the α-H of 1,4-dioxane to
2
2
generate a 1,4-dioxanyl radical. The 1,4-dioxanyl radical then undergoes a one electron
–
–
oxidation with I or IO /IO to generate an oxonium species. Reaction of the oxonium
2
2
species with carboxylate anion results in the α-acyloxy ether. Wan et al. indicated that
1
5b
TBHP/Bu NI system could lead to α-acyloxylation of THF using a carboxylic acid. The
4
inactivity of THF in the present reaction may be ascribed to low concentration of the
carboxylate anion.
1
2

ACCEPTED MANUSCRIPT
O
O
R
O
2 tBuO + RCOO
tBu
O
O
H
I2 or
IO or IO2
I
O
O
O
O
RCOO
O
O
R
O
O
Scheme 5. An alternative mechanism for the α-acyloxylation of ether
3
. Conclusion
We have demonstrated that Bu NI-catalyzed reaction of aldehydes with ethers or ketones can
4
be carried out using TBHP as the oxidant. A series of aldehydes including
aromatic/heteroaromatic aldehydes and functionalized aldehydes were employed. Cyclic and
acyclic diethers as well as propiophenones are suitable coupling partners. A crown ether,
1
2
,4,7,10-tetraoxacyclododecane, was also tested for the oxidative coupling.
-Arylacetaldehydes were demonstrated to react with diethers, but unexpectedly resulted in
α-aromatic acyloxy ethers. All reactions are metal-free and employed environmentally benign
oxidants and commercially available materials. This is a simple and straightforward
methodology for the synthesis of α-acyloxy ethers and α-acyloxy ketones.
4
4
. Experimental
.1. General remarks
The reactions were performed under nitrogen. Solvents and chemicals were purchased from
1
13
commercial venders and used as received. H and C NMR spectra were recorded at room
temperature on a Bruker av 300 or a Bruker av 400 spectrometer. The chemical shifts were
referenced to TMS or internal solvent resonances. High-resolution mass spectra (HR-MS)
were acquired on a Thermo Orbital XL ETD mass spectrometer (ESI or APCI).
4
.2. Typical procedure for the reaction of aldehydes with ethers or ketones
.2.1. Reaction of 4-bromobenzaldehydel with 1,4-dioxane (Table 1, entry 14). A
4
1
3

ACCEPTED MANUSCRIPT
Schlenk tube was charged with Bu NI (37 mg, 0.1 mmol), 4-bromobenzaldehydel (92 mg, 0.5
4
mmol), TBHP (0.73 mL, 5.5 M in decane, 4.01 mmol), and 1,4-dioxane (2 mL) under N2.
The mixture was stirred at 100 °C for 16 h. Volatiles were removed by rotary evaporation.
The residue was purified by column chromatography on silica gel (eluted using a 20:1
mixture of petroleum ether and EtOAc) to afford 1,4-dioxan-2-yl 4-bromobenzoate (112
mg, 78%).
4
.2.2. Reaction of 3-methoxybenzaldehyde with propiophenone (Table 4, entry 3). A
Schlenk tube was charged with Bu NI (37.0 mg, 0.10 mmol), propiophenone (67 mg, 0.5
4
mmol), 3-methoxybenzaldehyde (136.2 mg, 1.0 mmol) , TBHP (0.37 mL, 5.5 M in decane,
2
.03 mmol), and EtOAc (3 mL) under N . The mixture was stirred at 100 °C for 16 h.
2
Volatiles were removed by rotary evaporation. The residue was purified by column
chromatography on silica gel (eluted using a 10:1 mixture of petroleum ether and EtOAc) to
afford 1-oxo-1-phenylpropan-2-yl 3-methoxybenzoate (113.7 mg, 80%).
1
5b 1
1
,4-Dioxan-2-yl 4-bromobenzoate.
H NMR (400 MHz, CDCl ): δ 3.69 (dt, J = 2.4, 11.6
3
Hz, 1H, CH ), 3.84 (dd, J = 2.4, 6.8 Hz, 2H, CH ), 3.90 (d, J = 3 Hz, 2H, CH ), 4.16-4.25 (m,
2
2
2
1
H, CH ), 6.09 (s, 1H, CH), 7.61 (d, J = 8.4 Hz, 2H, C H ), 7.99 (d, J = 8.4 Hz, 2H, C H ).
2 6 4 6 4
1
3
C NMR (75 MHz, CDCl ): δ 61.87, 66.18, 67.84, 90.17, 128.68, 128.75, 131.48, 131.91,
3
1
64.59.
2
1 1
1
,4-Dioxan-2-yl 1-naphthoate. H NMR (300 MHz, CDCl ): δ 3.64-3.75 (m, 1H, CH ),
3 2
3
7
.78-3.88 (m, 2H, CH ), 3.90-4.01 (m, 2H, CH ), 4.21-4.29 (m, 1H, CH ), 6.20 (s, 1H, CH),
2 2 2
.46-7.55 (m, 2H, Ar), 7.59-7.65 (m, 1H, Ar), 7.87 (d, J = 8.1 Hz, 1H, Ar), 8.03 (d, J = 8.1
1
3
Hz, 1H, Ar), 8.34 (d, J = 7.5 Hz, 1H, Ar), 9.01 (d, J = 8.7 Hz, 1H, Ar). C NMR (75 MHz,
CDCl ): δ 62.01, 66.25, 68.04, 90.00, 124.54, 125.86, 126.30, 126.37, 128.10, 128.69,
3
1
31.00, 131.65, 133.96, 134.09, 165.98.
,4-Dioxan-2-yl 2-naphthoate. White solid, mp 90-91 °C. H NMR (300 MHz, CDCl ): δ
1
1
3
3
6
8
6
1
.64-3.76 (m, 1H, CH ), 3.79-3.89 (m, 2H, CH ), 3.94 (s, 2H, CH ), 4.20-4.35 (m, 1H, CH ),
2 2 2 2
.17 (s, 1H, CH), 7.51-7.61 (m, 2H, Ar), 7.85-7.90 (m, 2H, Ar), 7.97 (d, J = 7.5 Hz, 1H, Ar),
1
3
.13 (d, J = 7.8 Hz, 1H, Ar), 8.70 (s, 1H, Ar). C NMR (75 MHz, CDCl ): δ 61.90, 66.18,
3
7.94, 89.98, 125.34, 126.76, 127.00, 127.81, 128.30, 128.50, 129.45, 131.54, 132.49,
+
35.77, 165.39. HR-MS: m/z 281.07764 [M+Na] , calcd. for C H O Na 281.07843.
1
5
14
4
1
5b 1
1
,4-Dioxan-2-yl 4-methoxybenzoate.
H NMR (400 MHz, CDCl ): δ 3.65 (dt, J = 2.4, 12
3
Hz, 1H, CH ), 3.80 (dd, J = 2.8, 6.8 Hz, 2H, CH ), 3.84 (s, 3H, CH ), 3.86 (s, 2H, CH ), 4.14-
2
2
2
2
4
.24 (m, 1H, CH ), 6.05 (s, 1H, CH), 6.92 (d, J = 8.8 Hz, 2H, C H ), 8.06 (d, J = 8.8 Hz, 2H,
2 6 4
1
4

ACCEPTED MANUSCRIPT
1
3
C H ). C NMR (101 MHz, CDCl ): δ 55.51, 61.89, 66.20, 67.99, 89.57, 113.77, 122.11,
6
4
3
1
32.07, 163.82, 164.97.
,4-Dioxan-2-yl 3-phenoxybenzoate. Colorless liquid. H NMR (300 MHz, CDCl ): δ 3.66
1
1
3
(
dt, J = 2.1, 11.7 Hz, 1H, CH ), 3.81 (dd, J = 2.4, 6.6 Hz, 2H, CH ), 3.87 (d, J = 1.8 Hz, 2H,
2
2
CH ), 4.12- 4.26 (m, 1H, CH ), 6.08 (s, 1H, CH), 7.01 (d, J = 7.8 Hz, 2H, Ar), 7.13 (t, J = 7.4
2
2
Hz, 1H, Ar), 7.22 (dd, J = 1.5, 8.1 Hz, 1H, Ar), 7.31-7.45 (m, 3H, Ar), 7.77 (s, 1H, Ar), 7.87
1
3
(
d, J = 7.8 Hz, 1H, Ar). C NMR (75 MHz, CDCl ): δ 61.93, 66.18, 67.85, 90.20, 119.11,
3
1
20.18, 123.78, 123.86, 124.71, 129.92, 130.02, 131.68, 156.79, 157.59, 164.75. HR-MS:
+
m/z 323.08812 [M+Na] , calcd. for C H O Na 323.08899.
1
7
16
5
1
5b 1
1
,4-Dioxan-2-yl 4-acetamidobenzoate.
H NMR (300 MHz, CDCl ): δ 2.19 (s, 3H,
3
CH ), 3.65 (dt, J = 2.4, 11.7 Hz, 1H, CH ), 3.81 (dd, J = 2.1, 6.3 Hz, 2H, CH ), 3.87 (d, J =
3
2
2
1
8
8
.5 Hz, 2H, CH ), 4.13-4.24 (m, 1H, CH ), 6.06 (s, 1H, CH), 7.62 (d, J = 8.7 Hz, 2H, C H ),
2 2 6 4
13
.05 (d, J = 8.7 Hz, 2H, C H ). C NMR (75 MHz, CDCl ): δ 24.75, 61.92, 66.21, 67.96,
6
4
3
9.84, 119.01, 125.03, 131.26, 142.91, 151.67, 164.89, 168.99.
,4-Dioxan-2-yl biphenyl-4-carboxylate. White solid, mp 86-88 °C. H NMR (300 MHz,
CDCl ): δ 3.60-3.72 (m, 1H, CH ), 3.76-3.86 (m, 2H, CH ), 3.90 (s, 2H, CH ), 4.17-4.30 (m,
1
1
3
2
2
2
1
8
6
1
H, CH ), 6.12 (s, 1H, CH), 7.35-7.51 (m, 3H, Ar), 7.61 (d, J = 7.5 Hz, 2H, Ar), 7.67 (d, J =
2
1
3
.4 Hz, 2H, Ar) , 8.19 (d, J = 8.4 Hz, 2H, Ar). C NMR (75 MHz, CDCl ): δ 61.89, 66.19,
3
7.94, 89.92, 127.16, 127.34, 128.29, 128.53, 129.00, 130.50, 139.94, 146.17, 151.62,
+
65.13. HR-MS: m/z 307.09369 [M+Na] , calcd. for C H O Na 307.09408.
1
7
16
4
1
1
,4-Dioxan-2-yl methyl terephthalate. White solid, mp 108-109 °C. H NMR (400 MHz,
CDCl ): δ 3.70 (dt, J = 2, 11.6 Hz, 1H, CH ), 3.83-3.87 (m, 2H, CH ), 3.92 (d, J = 1.2 Hz,
3
2
2
2
2
6
H, CH ), 3.96 (s, 3H, CH ), 4.19-4.28 (m, 1H, CH ), 6.12 (s, 1H, CH), 8.12 (d, J = 8.4 Hz,
2 3 2
1
3
H, C H ), 8.19 (d, J = 8.4 Hz, 2H, C H ). C NMR (75 MHz, CDCl ): δ 52.52, 61.90,
6
4
6
4
3
6.19, 67.83, 90.38, 129.68, 129.93, 133.61, 134.42, 164.52, 166.23. HR-MS: m/z 289.06786
+
[
M+Na] , calcd. for C H O Na 289.06826.
1
3
14
6
2
1 1
1
,4-Dioxan-2-yl 4-(trifluoromethyl)benzoate. H NMR (300 MHz, CDCl ): δ 3.65-3.75
3
(
(
(
m, 1H, CH ), 3.85 (dd, J = 2.1, 6.3 Hz, 2H, CH ), 3.91 (d, J = 1.5 Hz, 2H, CH ), 4.16- 4.28
2 2 2
1
3
m, 1H, CH ), 6.12 (s, 1H, CH), 7.73 (d, J = 8.1 Hz, 2H), 8.24 (d, J = 8.1 Hz, 2H). C NMR
2
101 MHz, CDCl ): δ 61.88, 66.23, 67.83, 90.47, 123.68 (q, J = 273.8 Hz), 125.63 (q, J = 3.7
3
Hz), 130.43, 134.96 (q, J = 32.7 Hz), 133.08, 164.22.
1
5b 1
1
,4-Dioxan-2-yl 4-fluorobenzoate.
H NMR (300 MHz, CDCl ): δ 3.69 (dt, J = 2.4, 11.7
3
Hz, 1H, CH ), 3.84 (dd, J = 2.1, 6.6 Hz, 2H, CH ), 3.90 (d, J = 1.8 Hz, 2H, CH ), 4.15-4.28
2
2
2
13
(
m, 1H, CH ), 6.09 (s, 1H, CH), 7.14 (t, J = 8.6 Hz, 2H, C H ), 8.12-8.18 (m, 2H, C H ). C
2 6 4 6 4
1
5

ACCEPTED MANUSCRIPT
NMR (75 MHz, CDCl ): δ 61.85, 66.20, 67.88, 90.00, 115.73 (d, J = 22.1 Hz), 126.04 (d, J =
3
2
.9 Hz), 132.59 (d, J = 9.4 Hz), 164.18, 166.11 (d, J = 254.8 Hz).
1
5b 1
1
,4-Dioxan-2-yl 4-chlorobenzoate.
H NMR (300 MHz, CDCl ): δ 3.68 (dt, J = 2.4, 11.7
3
Hz, 1H, CH ), 3.83 (dd, J = 2.4, 6.6 Hz, 2H, CH ), 3.89 (d, J = 1.8 Hz, 2H, CH ), 4.15- 4.27
2
2
2
(
m, 1H, CH ), 6.09 (s, 1H, CH), 7.44 (d, J = 8.4 Hz, 2H, C H ), 8.06 (d, J = 8.4 Hz, 2H,
2
6
4
1
3
C H ). C NMR (75 MHz, CDCl ): δ 61.89, 66.19, 67.86, 90.16, 128.30, 128.91, 131.37,
6
4
3
1
39.98, 164.44.
Di(1,4-dioxan-2-yl) terephthalate. White solid, mp 124-126 °C. H NMR (400 MHz,
CDCl ): δ 3.65 (dt, J = 2.4, 11.6 Hz, 2H, CH ), 3.78-3.83 (m, 4H, CH ), 3.87 (s, 4H, CH ),
1
3
2
2
2
1
3
4
.14-4.23 (m, 2H, CH ), 6.08 (s, 2H, CH), 8.16 (s, 4H, C H ). C NMR (101 MHz ,CDCl ): δ
2 6 4 3
+
6
1.78, 66.09, 90.31, 129.92, 133.90, 164.38. HR-MS: m/z 361.08932 [M+Na] , calcd. for
C H O Na 361.08939.
16
18
8
1
5b 1
1
,4-Dioxan-2-yl thiophene-2-carboxylate.
H NMR (300 MHz, CDCl ): δ 3.67 (d, J =
3
1
1.4 Hz, 1H, CH ), 3.75-3.95 (m, 4H, CH ), 4.12-4.28 (m, 1H, CH ), 6.06 (s, 1H, CH), 7.13
2
2
2
1
3
(
s, 1H, C H S), 7.56-7.69 (m, 1H, C H S), 7.90 (s, 1H, C H S). C NMR (75 MHz, CDCl ):
4 3 4 3 4 3 3
δ 61.79, 66.07, 67.73, 89.95, 127.93, 133.25, 134.22, 160.86.
2
1 1
1
,4-Dioxan-2-yl furan-2-carboxylate. H NMR (400 MHz, CDCl ): δ 3.67 (dt, J = 2.4,
3
1
1.6 Hz, 1H, CH ), 3.80-3.84 (m, 2H, CH ), 3.87 (d, J = 1.6 Hz, 2H, CH ), 4.16-4.25 (m, 1H,
2 2 2
CH ), 6.07 (s, 1H, CH), 6.55 (dd, J = 1.6, 3.2 Hz, 1H, C H O), 7.31 (d, J = 3.2 Hz, 1H,
2
4
3
13
C H O), 7.62-7.65 (m, 1H, C H O). C NMR (101 MHz, CDCl ): δ 61.74, 66.06, 67.71,
4
3
4
3
3
8
9.81, 112.01, 118.99, 144.10, 146.96, 157.27.
2
2
1
1
,4-Dioxan-2-ylcinnamate. Pale yellow oil. H NMR (400 MHz, CDCl ): δ 3.66 (dt, J =
3
2
1
.8, 12 Hz, 1H, CH ), 3.79-3.84 (m, 4H, CH ), 4.14-4.23 (m, 1H, CH ), 5.99 (t, J = 1.6 Hz,
2 2 2
H, CH), 6.51 (d, J = 16 Hz, 1H, =CH), 7.36-7.41 (m, 3H, Ph), 7.51-7.56 (m, 2H, Ph), 7.78
1
3
(
d, J = 16 Hz, 1H, =CH). C NMR (101 MHz, CDCl ): δ 61.81, 66.20, 67.96, 89.45, 117.54,
3
1
28.30, 129.02, 130.65, 134.27, 146.15, 165.59.
2
1 1
1
,4-Dioxan-2-yl benzoate. H NMR (400 MHz, CDCl ): δ 3.69 (dt, J = 2.4, 12 Hz, 1H,
3
CH ), 3.84 (dd, J = 2.4, 6.8 Hz, 2H, CH ), 3.90 (d, J = 1.6 Hz, 2H, CH ), 4.19- 4.28 (m, 1H,
2
2
2
CH ), 6.11 (s, 1H, CH), 7.47 (t, J = 7.6 Hz, 2H, Ph), 7.60 (t, J = 7.4 Hz, 1H, Ph), 8.11-8.17
2
1
3
(
m, 2H, Ph). C NMR (101 MHz, CDCl ): δ 61.89, 66.25, 67.96, 89.91, 128.56, 129.81,
3
1
30.02, 133.53, 165.35.
,3-Dioxolan-4-yl 4-bromobenzoate. Pale yellow oil. H NMR (400 MHz, CDCl ): δ
1
1
3
4
7
.11-4.19 (m, 2H, CH ), 5.15 (s, 1H, CH ), 5.20 (s, 1H, CH ), 6.58 (dd, J = 2, 4 Hz, 1H, CH),
2 2 2
13
.59 (d, J = 8.4 Hz, 2H, C H ), 7.91 (d, J = 8.4 Hz, 2H, C H ). C NMR (101 MHz, CDCl ):
6
4
6
4
3
1
6

ACCEPTED MANUSCRIPT
δ 70.82, 94.98, 96.17, 128.44, 128.89, 131.42, 131.98, 165.27. HR-MS: m/z 294.95721
+
[
M+Na] , calcd. for C H O BrNa 294.95764.
1
0
9
4
1
(
Methoxymethoxy)methyl 4-bromobenzoate. Colorless liquid. H NMR (400 MHz, CDCl ):
3
δ 3.34 (s, 3H, CH ), 4.76 (s, 2H, CH ), 5.52 (s, 2H, CH ), 7.52 (d, J = 8.6 Hz, 2H, C H ), 7.86
3
2
2
6
4
1
3
(
d, J = 8.6 Hz, 2H, C H ). C NMR (101 MHz, CDCl ): δ 56.19, 86.07, 95.38, 128.66,
6 4 3
+
1
28.74, 131.42, 131.94, 165.35. HR-MS: m/z 296.97278 [M+Na] , calcd. for C H O BrNa
10 11 4
2
96.97329.
,2-Dimethoxyethyl 4-bromobenzoate.
OCH ), 3.54 (s, 3H, OCH ), 3.59-3.66 (m, 2H, CH ), 6.12 (t, J = 4.8 Hz, 1H ,CH), 7.60 (d, J
2
1 1
1
H NMR (400 MHz, CDCl ): δ 3.43 (s, 3H,
3
3
3
2
13
=
8.4 Hz, 2H, C H ), 7.95 (d, J = 8.4 Hz, 2H, C H ). C NMR (101 MHz, CDCl ): δ 57.48,
6 4 6 4 3
5
9.73, 72.84, 97.90, 128.62, 128.73, 131.52, 131.96, 165.59.
2
1 1
(
2-Methoxyethoxy)methyl 4-bromobenzoate. H NMR (400 MHz, CDCl ): δ 3.38 (s, 3H,
3
OCH ), 3.56-3.61 (m, 2H, CH ), 3.86-3.91 (m, 2H, CH ), 5.58 (s, 2H, CH ), 7.60 (d, J = 8.6
3
2
2
2
1
3
Hz, 2H, C H ), 7.94 (d, J = 8.6 Hz, 2H, C H ). C NMR (101 MHz , CDCl ): δ 59.22, 69.92,
6
4
6
4
3
7
1.63, 90.35, 125.58, 128.87, 131.43, 131.92, 165.44.
,4,7,10-Tetraoxacyclododecan-2-yl 4-bromobenzoate. White solid, mp 70-72 °C. H
NMR (400 MHz, CDCl ): δ 3.59-3.85 (m, 12H, CH ), 3.89-3.94 (m, 1H, CH ), 4.01-4.08 (m,
1
1
3
2
2
1
H, CH ), 6.38 (dd, J = 3.6, 7.2 Hz, 1H, CH), 7.57 (d, J = 8.5 Hz, 2H, Ar), 7.91 (d, J = 8.5
2
1
3
Hz, 2H, Ar). C NMR (101 MHz, CDCl ): δ 70.25, 70.52, 70.58, 70.77, 71.15, 71.18, 71.41,
3
+
9
8.01, 128.56, 128.76, 131.31, 131.46, 131.85, 165.58. HR-MS: m/z 397.02509 [M+Na] ,
calcd. for C H O BrNa 397.02572.
1
5
19
6
1
1
-Oxo-1-phenylpropan-2-yl 3-methoxybenzoate. Pale yellow liquids. H NMR (400 MHz,
CDCl ): δ 1.67 (d, J = 6.8 Hz, 3H, CH ), 3.84 (s, 3H, OCH ), 6.20 (q, J = 6.8 Hz, 1H, CH),
3
3
3
7
7
.12 (dd, J = 2.8, 8.4 Hz, 1H, Ar), 7.35 (t, J = 8 Hz, 1H, Ar), 7.49 (t, J = 7.6 Hz, 2H, Ar) ,
1
3
.56-7.62 (m, 2H, Ar), 7.70 (d, J = 8 Hz, 1H, Ar), 7.98-8.03 (m, 2H, Ar). C NMR (101
MHz, CDCl ): δ 17.29, 55.55, 72.13, 114.32, 120.01, 122.43, 128.63, 128.93, 129.56, 130.86,
3
+
1
33.71, 134.57, 159.66, 166.00, 196.84. HR-MS: m/z 285.11136 [M+H] , calcd. for
C H O 285.11214.
17
17
4
1
1
-Oxo-1-phenylpropan-2-yl 4-acetamidobenzoate. White solid, mp 184-186 °C. H
NMR(400 MHz, CDCl ): δ 1.67 (d, J = 7.2 Hz, 3H, CH ), 2.21 (s, 3H, CH ), 6.18 (q, J = 7.2
3
3
3
Hz, 1H, CH), 7.36 (b, 1H, NH), 7.49 (t, J = 7.6 Hz, 2H, Ph), 7.59 (d, J = 7.6 Hz, 3H, Ph),
13
8
.00 (d, J = 8.8 Hz, 2H, C H ), 8.05 (d, J = 8.8 Hz, 2H, C H ). C NMR (101 MHz ,CDCl ):
6 4 6 4 3
δ 17.39, 24.84, 71.95, 118.88, 124.66, 128.66, 129.00, 131.21, 133.89, 134.49, 142.76,
+
1
65.65, 168.84, 197.50. HR-MS: m/z 312.12219 [M+H] , calcd. for C H O N 312.12303.
1
8
18
4
1
7

ACCEPTED MANUSCRIPT
1
1
-Oxo-1-phenylpropan-2-yl 2-naphthoate. Pale yellow solid, mp 108-110 °C. H NMR
(
400 MHz, CDCl ): δ 1.73 (d, J = 7.2 Hz, 3H, CH ), 6.27 (q, J = 7.2 Hz, 1H, CH), 7.47-7.61
3
3
(m, 5H, Ar), 7.86-7.89 (m, 2H, Ar), 7.95 (d, J = 8 Hz, 1H, Ar), 8.01-8.05 (m, 2H, Ar),
1
3
8
1
1
.07-8.12 (m, 2H, Ar), 8.68 (s, 1H, Ar). C NMR (101 MHz, CDCl ): δ 17.40, 72.14,
3
25.44, 126.80, 126.85, 127.90, 128.33, 128.52, 128.68, 128.95, 129.56, 131.65, 132.57,
+
33.73, 134.64, 135.83, 166.26, 196.93. HR-MS: m/z 305.11661 [M+H] , calcd. for
C H O 305.11722.
20
17
3
1
1
-Oxo-1-phenylpropan-2-yl thiophene-2-carboxylate. Pale yellow liquid. H NMR (400
MHz, CDCl ): δ 1.66 (d, J = 7.2 Hz, 3H, CH ), 6.16 (q, J = 7.2 Hz, 1H, CH), 7.11 (t, J = 4.4
3
3
Hz, 1H, C H S), 7.49 (t, J = 7.6 Hz, 2H, Ph), 7.56-7.63 (m, 2H, Ph+C H S), 7.86 (d, J = 3.6
4
3
4
3
1
3
Hz, 1H, C H S), 7.99 (d, J = 8 Hz, 2H, Ph). C NMR (101 MHz, CDCl ): δ 17.32, 72.25,
4
3
3
1
27.95, 128.67, 128.92, 133.02, 133.13, 133.72, 134.25, 134.52, 161.67, 196.63. HR-MS:
+
m/z 261.05722 [M+H] , calcd. for C H O S 261.05799.
1
4
13
3
1
Methyl 1-oxo-1-phenylpropan-2-yl terephthalate. Pale yellow solid, mp 114-115 °C. H
NMR (400 MHz, CDCl ): δ 1.70 (d, J = 7.2 Hz, 3H, CH ), 3.95 (s, 3H, OCH ), 6.23 (q, J =
3
3
3
7
.2 Hz, 1H, CH), 7.50 (t, J = 7.8 Hz, 2H, Ph), 7.61 (t, J = 7.4 Hz, 1H, Ph), 8.01 (d, J = 8 Hz,
1
3
2
H, Ph), 8.11 (d, J = 8.4 Hz, 2H, C H ), 8.17 (d, J = 8.4 Hz, 2H, C H ). C NMR (101 MHz,
6
4
6
4
CDCl ): δ 17.36, 52.58, 72.42, 128.61, 128.98, 129.68, 129.95, 133.36, 133.85, 134.29,
3
+
1
3
34.37, 165.29, 166.34, 196.49. HR-MS: m/z 313.10648 [M+H] , calcd. for C H O ,
1
8
17
5
13.10705.
-Oxo-1-phenylpropan-2-yl cyclohexanecarboxylate. Colorless liquid. H NMR (CDCl ): δ
1
1
3
1
1
1
7
2
.17-1.34 (m, 3H, CH ), 1.39-1.49 (m, 2H, CH ), 1.51 (d, J = 7 Hz, 3H, CH ), 1.59-1.67 (m,
2 2 3
H, CH ), 1.71-1.78 (m, 2H, CH ), 1.93 (t, J = 13.4 Hz, 2H, CH ), 2.40 (tt, J = 3.6, 11.2 Hz,
2
2
2
H, CH), 5.95 (q, J = 7 Hz, 1H), 7.47 (t, J = 7.6 Hz, 2H, Ph), 7.58 (t, J = 7.4 Hz, 1H, Ph),
13
.91-7.94 (m, 2H, Ph). C NMR (101 MHz, CDCl ): δ 17.10, 25.45, 25.48, 25.85, 28.94,
3
9.04, 42.92, 71.05, 128.59, 128.85, 133.59, 134.72, 175.60, 197.28. HR-MS: m/z 261.14783
+
[
M+H] , calcd. for C H O 261.14852.
1
6
21
3
1
-(4-Methoxyphenyl)-1-oxopropan-2-yl 3-methoxybenzoate. Pale yellow solid, mp 84-86
1
°
C. H NMR (400 MHz, CDCl ): δ 1.66 (d, J = 7.2 Hz, 3H, CH ), 3.84 (s, 3H, OCH ), 3.87
3
3
3
(
s, 3H, OCH ), 6.16 (q, J = 7.2 Hz, 1H, CH), 6.96 (d, J = 8.8 Hz, 2H, Ar), 7.09-7.14 (m, 1H,
3
Ar), 7.35 (t, J = 8 Hz, 1H, Ar), 7.58-7.62 (m, 1H, Ar), 7.70 (d, J = 7.6 Hz, 1H, Ar), 8.00 (d, J
1
3
=
8.8 Hz, 2H, Ar). C NMR (101 MHz, CDCl ): δ 17.49, 55.58, 55.64, 71.91, 114.16,
3
1
14.35, 119.99, 122.47, 127.46, 129.55, 131.03, 159.68, 164.03, 166.03, 195.18. HR-MS:
+
m/z 315.12195 [M+H] , calcd. for C H O 315.12270.
1
8
19
5
1
8

ACCEPTED MANUSCRIPT
1
1
-Oxo-1-phenylbutan-2-yl 3-methoxybenzoate. Pale yellow liquid. H NMR (400 MHz,
CDCl ): δ 1.12 (t, J = 7.6 Hz, 3H, CH ), 1.97-2.14 (m, 2H, CH ), 3.84 (s, 3H, OCH ), 6.04
3
3
2
3
(dd, J = 4.8, 8 Hz, 1H, CH), 7.12 (dd, J = 2, 7.6 Hz, 1H, Ar), 7.36 (t, J = 7.8 Hz, 1H, Ar),
7
2
1
2
.48 (t, J = 7.8 Hz, 2H, Ar), 7.57-7.62 (m, 2H, Ar), 7.72 (d, J = 8 Hz, 1H, Ar), 7.98-8.03 (m,
1
3
H, Ar). C NMR (101 MHz, CDCl ): δ 10.09, 25.02, 55.53, 76.98, 114.42, 119.86, 122.38,
3
28.53, 128.90, 129.56, 130.97, 133.63, 135.05, 159.67, 166.20, 196.47. HR-MS: m/z
+
99.12726 [M+H] , calcd. for C H O 299.12779.
1
8
19
4
1
Bis(1-oxo-1-phenylpropan-2-yl) terephthalate. White solid, mp 146-148 °C. H NMR (400
MHz, CDCl ): δ 1.70 (d, J = 7.2 Hz, 6H, CH ), 6.23 (q, J = 7.2 Hz, 2H, CH), 7.49 (t, J = 7.6
3
3
1
3
Hz, 4H, Ph), 7.60 (t, J = 7.4 Hz, 2H, Ph), 8.00 (d, J = 7.6 Hz, 4H, Ph), 8.17 (s, 4H, C H ). C
6
4
NMR (101 MHz, CDCl ): δ 17.34, 72.50, 128.60, 128.97, 129.96, 133.69, 133.82, 134.43,
3
+
1
65.25, 196.50. HR-MS: m/z 453.13043 [M+Na] , calcd. for C H O Na 453.13086.
2
6
22
6
1
2
,2,6,6-Tetramethylpiperidin-1-yl 4-bromobenzoate. White solid, mp 104-106 °C. H NMR
(
CDCl ): δ 1.08 (s, 6H, CH ), 1.23 (s, 6H, CH ), 1.39-1.46 (m, 1H, CH ), 1.51-1.60 (m, 2H,
3
3
3
2
CH ), 1.62-1.80 (m, 3H, CH ), 7.57 (d, J = 8.4 Hz, 2H, C H ), 7.91 (d, J = 8.4 Hz, 2H, C H ).
2
2
6
4
6
4
1
3
C NMR (101 MHz, CDCl ): δ 16.92, 20.80, 31.90, 38.98, 60.41, 127.91, 128.49, 131.02,
3
+
1
31.76, 165.61. HR-MS: m/z 340.09024 [M+H] , calcd. for C H O NBr 340.09067.
1
6
23
2
Acknowledgment
This research was supported by the National Natural Science Foundation of China (grant no.
1172208). We thank Dr. R. S. McIsaac for the grammatical edits.
2
Supplementary data
Supplementary data associated with this article can be found in the online version, at
http://dx.doi.org/xxxxxx.
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Supplementary data
Bu NI-catalyzed α-acyloxylation reaction of ethers and ketones
4
with aldehydes and tert-butyl hydroperoxide
Feng Zhu, Zhong-Xia Wang*
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, People’s
Republic of China
1
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H and C NMR spectral copies of all products.
1

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(
1) 1,4-Dioxan-2-yl 4-bromobenzoate
2

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(
2) 1,4-Dioxan-2-yl 1-naphthoate
3

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(
3) 1,4-Dioxan-2-yl 2-naphthoate
4

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(
4) 1,4-Dioxan-2-yl 4-methoxybenzoate
5

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(
5) 1,4-Dioxan-2-yl 3-phenoxybenzoate
6

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(
6) 1,4-Dioxan-2-yl 4-acetamidobenzoate
7