Tuning Regioselectivity of Wacker Oxidation in One Catalytic System: Small Change Makes Big Step

Article abstract of DOI:10.1021/acs.joc.8b01547

A regioselectivity switchable aerobic Wacker-Tsuji oxidation has been developed using catalytic tert-butyl nitrite as a simple organic redox cocatalyst. By solely switching the solvent, either substituted aldehydes or ketones could be prepared under mild

Full text of DOI:10.1021/acs.joc.8b01547

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Note
Tuning Regioselectivity of Wacker Oxidation in One
Catalytic System: Small Change Makes Big Step
Kang-Fei Hu, Xiao-Shan Ning, Jian-Ping Qu, and Yan-Biao Kang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01547 • Publication Date (Web): 14 Aug 2018
Downloaded from http://pubs.acs.org on August 14, 2018
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The Journal of Organic Chemistry
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Tuning Regioselectivity of Wacker Oxidation in One Catalytic Sys-
tem: Small Change Makes Big Step
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†
§
†§
‡*
†*
Kang-Fei Hu, Xiao-Shan Ning, Jian-Ping Qu, and Yan-Biao Kang
†
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China
‡
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innova-
tion Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
Supporting Information Placeholder
ABSTRACT: A regioselectivity switchable aerobic Wacker–Tsuji oxidation has been developed using catalytic tert-butyl ni-
trite as a simple organic redox cocatalyst. By solely switching the solvent, either substituted aldehydes or ketones could be
prepared under mild aerobic conditions in good yields, respectively. A mechanistic explanation for the selectivity control is
proposed.
The oxidation of terminal olefins to carbonyl compounds
with palladium(II) chloride and copper(I) chloride in the
presence of air, known as Wacker-Tsuji oxidation, has
organic NO-source which might replace inorganic NO -
salts in catalysis. We then developed an aldehyde-selec-
2
1
0c
1
tive aerobic Wacker–Tsuji oxidation using tert-butyl nitrite
1
0a
proven to be a powerful tool in synthetic chemistry due to
its practicability, efficiency and broad functional group
as a simple organic redox cocatalyst. During our investi-
gations, we found that the solvent is crucial to the regiose-
lectivity control of aerobic Wacker-Tsuji oxidation. After
careful studies, we realized a ketone/aldehyde selectivity
controllable Wacker-Tsuji oxidation by just switching sol-
vent (Scheme 2B). Herein we present this result in details.
2-4
compatibility (Scheme 1). Traditional Wacker-Tsuji oxi-
dation usually proceeds in wet DMF, which follows Markov-
nikov’s rule to yield ketones as the major products, whereas
the anti-Markovnikov selective oxidation for the direct syn-
thesis of aldehyde is highly desirable and attracted a lot of
Scheme 1. Wacker-Tsuji Oxidation Catalyzed by Pd-Cu
System
5-9
research interest. The anti-Markovnikov oxidation has
been realized by the using directing of functional group on
6
5
the olefins or steric effects of solvents. Thus, different
strategies or methods have been applied to accomplish ke-
tones or aldehydes.
Scheme 2. Site-Selectivity Control with One Catalytic
System
The switch of such selectivity solely via tiny change of the
reaction conditions in one catalytic system would be very
valuable to achieve different targets for different purposes
in organic synthesis. However, the development of regiose-
lectivity-switchable Wacker-Tsuji oxidation has always
been a challenge. The ketone-selective Wacker oxidation is
a
thermodynamic controlled Markovnikov process,
whereas the aldehyde-selectivity is kinetically controlled
anti-Markovnikov process. Even several individual exam-
ples have been involved with the accomplishment of the ke-
3
8
tone- or aldehyde-selective Wacker oxidation; there are
few examples on the efficient control of the regioselectivity
of Wacker oxidation (Scheme 2A).
In our research concerning ammoxidation of
1
0b
t
methylarenes, we noticed that BuONO was a convenient
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We first choose (but-3-en-1-yloxy)benzene 1a as model
Page 2 of 7
smoothly giving the desired ketones and aldehydes in up to
90% yields and up to 13.5:1 selectivity (2i–j, and 3i–j). A
drawback for this method is that styrene and 1-octene are
not suitable for aldehyde-selectivity and only ketone prod-
ucts are obtained.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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5
6
substrate in the aerobic oxidation with BuONO as a redox
t
cocatalyst using Pd(PhCN)
2
Cl
2
as catalyst to investigate var-
t
ious solvents (Table 1, entries 1-5). When BuOH was used,
aldehyde product 3a was obtained in 80% yield with 15%
ketone product 2a (entry 1). Yield of aldehyde 3a decreases
as the substituent on alcohol becomes smaller (entries 2-5).
But EtOH gives the highest yield of ketone 2a (entry 4). The
addition of water (2.0 equivalent) suppresses aldehyde
product 3a and improves the yield of ketone 2a to 76% (en-
Scheme 3. Reaction Scopea
t
try 4 vs 6). Reducing the loading of BuONO results in the
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
decreased yield of 2a (entries 7-8), while increasing the
loading of BuONO does not affect the yield of 2a (entries 9-
t
11). Other catalyst, such as Pd(CH
3
CN)
2
Cl
2
, PdCl
2
, Pd(OAc) ,
2
were also employed but did not improve of yield of 2a (en-
tries 12-14).
Table 1. Reaction Conditionsa
t(h) 2ab
3ab
en-
try
[Pd]
x
sol-
vent
1
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
Pd(PhCN)
2
2
2
2
2
2
2
2
2
2
2
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
2
2
20
20
20
20
20
20
0
tBuOH
nBuOH 11
1
15
36
55
67
44
76
6
80
2
64
3
2
iPrOH
EtOH
MeOH
EtOH
EtOH
EtOH
EtOH
EtOH
1
45
4
2
1
30
5
2
1
23
6c
7c
8c
9c
0.5
24
1.5
0.5
0.5
0.5
2
24
2
2
trace
36
2
10
30
50
61
75
77
74
61
55
20
2
25
1
0c
1
1c
1
2c
1
3c
1
4c
23
2
2
100 EtOH
21
Pd(CH
PdCl
Pd(OAc)
3
CN)
2
Cl
2
20
20
20
EtOH
EtOH
EtOH
23
2
24
24
11
2
trace
a
b
Reaction conditions: 1a (0.5 mmol), solvent (2 mL). 2a/3a
1
t
was determined by H NMR using CH
standard. H
3
NO , BuOMe as internal
2
c
2
O (2.0 equiv) was used as additive.
After establishing the optimized reaction conditions (7.5
t
mol % of Pd(PhCN)
2
Cl
2
, 20 mol % BuONO, using either
a
t
Conditions: 1 (0.5 mmol), Pd(PhCN)
2
Cl
BuONO (20 mol %), BuOH (2 mL) or EtOH (2 mL with 2 equiv
O), O (1 atm). Ratio (K/A or A/K) refers to Aldehyde and
Ketone.
2
(7.5 mol %),
BuOH or EtOH as solvent), the scope of ketone/aldehyde-
t
t
selectivity switchable Wacker–Tsuji oxidation is evaluated
H
2
2
(
Scheme 3). Various terminal alkenes bearing different
functional groups were subjected to the optimized condi-
tions and ketone 2 and aldehyde 3 were obtained with as
high as 13.8:1 regioselectivity in generally good to high iso-
lated yields. Various functional groups or protecting groups
could be tolerated under this reaction conditions. For exam-
ple, ketone 2b and aldehyde 3b bearing phenyl ether
groups were isolated in 78% and 73% yields with good re-
gioselectivity. The ester groups are tolerated in this reaction
A plausible mechanism for site-selectivity switchable
Wacker–Tsuji oxidation is proposed (Scheme 4). Pd(II) co-
ordinates with alkene 1 to form intermediate A which is at-
tacked by the alcohol solvent to generate intermediate B.
The β–elimination affords enol ether D or Dꞌ. For bulky sol-
vent BuOH aldehyde 3 is obtained whereas for smaller al-
cohol EtOH ketone 2 is achieved. Catalytically active Pd(II)
t
(2c-f and 3c-f). The ether protecting groups such as TBDPS
species is regenerated by the oxidation of NO which is in
2
and methyl group kept unchanged in this oxidation (2g–h
and 3g–h). Even nitrogen-containing substrates reacted
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The Journal of Organic Chemistry
1
situ produced from the oxidation of NO with molecular ox-
ygen. BuONO is the donor of NO and thus plays the role of
redox cocatalyst.
mg, 80%. H NMR (400 MHz, CDCl
3
) δ 7.30-7.26 (m, 2 H),
1
2
3
4
5
6
7
8
9
t
6.96 (d, J = 7.2 Hz, 1 H), 6.93-6.89 (m, 2 H), 4.23 (t, J = 6.4 Hz,
2 H), 2.91 (t, J = 6.4 Hz, 2 H), 2.25 (s, 3 H). C{ H} NMR (100
1
3
1
MHz, CDCl
30.9.
3
) δ 206.8, 158.9, 129.8, 121.3, 114.9, 63.1, 43.3,
Scheme 4. Proposed Mechanism
5-phenoxypentan-2-one (2b).11 This compound was pre-
pared according to the general procedure, purified by flash
column chromatography (PE/EA = 40/1), as yellow
solid(69.5 mg, 78%. H NMR (400 MHz, CDCl
1
3
) δ 7.30-7.28
(
m, 2 H), 6.94 (t, J = 7.2 Hz, 1 H), 6.88 (d, J = 8.0 Hz, 2 H), 3.97
(t, J = 6.0 Hz, 2 H), 2.66 (t, J = 7.2 Hz, 2 H), 2.18 (s, 3 H), 2.09-
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
1
2
1
.03 (m, 2 H). C{ H} NMR (100 MHz, CDCl
29.8, 121.0, 114.7, 66.9, 40.3, 30.4, 23.7.
3
) δ 208.7, 159.1,
3
-oxobutyl benzoate (2c).12 This compound was prepared
according to the general procedure, purified by flash col-
umn chromatography (PE/EA = 20/1), yellow oil, 71.1mg,
1
7
4%. H NMR (400 MHz, CDCl
3
) δ 8.00 (d, J = 7.6 Hz, 2 H),
7.55 (t, J = 7.6 Hz, 1 H), 7.42 (t, J = 7.6 Hz, 2 H), 4.58 (t, J = 6.0
1
3
1
Hz, 2 H), 2.90 (t, J = 6.0 Hz, 2 H), 2.23 (s, 3 H). C{ H} NMR
100 MHz, CDCl ) δ 206.0, 166.7, 133.4, 130.3, 129.9, 128.7,
0.1, 42.7, 30.6.
-oxopentyl benzoate (2d).13 This compound was pre-
(
6
3
4
pared according to the general procedure, purified by flash
column chromatography (PE/EA = 20/1), as yellow oil (70.4
In conclusion, we have developed regioselectivity con-
trollable aerobic Wacker–Tsuji oxidation at room tempera-
ture under copper- or silver-free conditions. Catalytic
amount of tert-butyl nitrite worked as a simple organic re-
dox cocatalyst. A variety of aldehydes and ketones were
achieved in generally high regioselectivity as well as good
to high yields.
1
mg, 68%. H NMR (400 MHz, CDCl ) δ 8.03 (d, J = 8.0 Hz, 2
3
H), 7.56 (t, J = 7.6 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 2 H), 4.33 (t, J
= 6.4 Hz, 2 H), 2.60 (t, J = 7.0 Hz, 2 H), 2.17 (s, 3 H), 2.09-2.02
1
3
1
(m, 2 H). C{ H} NMR (100 MHz, CDCl ) δ 208.1, 166.9,
3
133.3, 130.5, 129.9, 128.7, 64.4, 40.3, 30.4, 23.2.
methyl 2-(3-chlorophenyl)-4-oxopentanoate (2e). This
compound was prepared according to the general
procedure, purified by flash column chromatography
EXPERIMENTAL SECTION
General Information. Solvents were pre-dried over acti-
vated MS 4Å and heated to reflux over sodium (for toluene
and THF) or calcium hydride (for CH
1
(PE/EA = 20/1 ), yellow oil, 86.4 mg, 74%. H NMR (400
MHz, CDCl
3
) δ 7.27-7.26 (m, 3 H), 7.16 (s, 1 H), 4.09 (dd, J =
2
Cl
2
) under a nitrogen
10.0, 4.0 Hz, 1 H), 3.68 (s, 3 H), 3.39 (dd, J = 18.0, 10.0 Hz, 1
1
atmosphere and collected by distillation. H NMR (400
13
1
H), 2.73 (dd, J = 18.0, 4.0 Hz, 1 H), 2.20 (s, 3 H). C{ H} NMR
100 MHz, CDCl ) δ 206.0, 173.5, 140.3, 134.9, 130.4, 128.2,
28.1, 126.4, 52.8, 47.1, 46.0, 30.2. HRMS (ESI-TOF) m/z:
13
1
MHz) and C{ H} NMR (100 MHz) spectra were recorded
(
3
on a Bruker spectrometer. Chemical shifts are reported in δ
1
1
1
13
units relative to (TMS, H δ = 0; CDCl
3
, H δ = 7.26, C δ =
+
[M+Na] Calcd for C12
H
13ClO Na 263.0451; Found 263.0454.
3
77.36).
3
-oxo-1-phenylbutyl acetate (2f).14 This compound was
General procedure for Markovnikov selective Wacker
prepared according to the general procedure, purified by
flash column chromatography (PE/EA = 10/1), as yellow oil
t
oxidation under Pd- BuONO-O
2
-system in wet EtOH.
Pd(PhCN)
2
Cl
2
(14.4 mg, 0.0375 mmol) was weighed directly
1
(
72.2 mg, 70%. H NMR (400 MHz, CDCl
3
) δ 7.35-7.32 (m, 3
into a 25 mL Schlenk tube and dried under high vacuum for
H), 7.31-7.29 (m, 1 H), 6.18 (dd, J= 8.8, 5.2 Hz, 1 H), 3.12 (dd,
J = 16.8, 8.8 Hz, 1 H), 2.82 (dd, J = 16.8, 5.2 Hz, 1 H), 2.15 (s,
20 min. Under an atmosphere of oxygen (1 atm, balloon),
t
EtOH (2 mL), H
2
O (1.0 mmol) and BuONO (10.3 mg, 0.1
13
1
3
1
H), 2.03 (s, 3 H). C{ H} NMR (100 MHz, CDCl ) δ 204.8,
70.0, 139.8, 128.8, 128.4, 126.6, 71.7, 50.0, 30.6, 21.2.
3
o
mmol) were added and stirred at 25 C. Alkene (0.5 mmol)
was then added and the resulting reaction mixture was
monitored by TLC. After completion, the reaction was
quenched by addition of water (5 mL) and extracted three
4-((tert-butyldiphenylsilyl)oxy)butan-2-one (2g). This
compound was prepared according to the general proce-
dure, purified by flash column chromatography (PE/EA =
times with CH
sequently washed with brine and dried over Na
2
Cl
2
. The combined organic layers were sub-
SO . The or-
1
40/1 ), as yellow oil (133.9 mg, 82%. H NMR (400 MHz,
CDCl ) δ 7.66 (dd, J = 8.0, 1.6 Hz, 4 H), 7.45-7.37 (m, 6 H),
3.94 (t, J = 6.4 Hz, 2 H), 2.64 (t, J = 6.4 Hz, 2 H), 2.19 (s, 3 H),
2
4
ganic solvent was removed under reduced pressure then
the crude mixture was examined on H NMR spectrometer
3
1
1
3
to determine the conversion and selectivity using tert-butyl
methyl ether (with nitromethane as a dual standard) as in-
ternal standard. The crude product was purified by chroma-
tography on silica gel to afford the corresponding products.
4-phenoxybutan-2-one (2a).10a This compound was pre-
pared according to the general procedure, purified by flash
column chromatography (PE/EA = 40/1), yellow oil, 65.7
1.03 (s, 9 H). C NMR (100 MHz, CDCl ) δ 208.3, 135.9,
133.8, 130.1, 128.1, 60.0, 46.7, 31.1, 27.1, 19.5. HRMS (ESI-
TOF) m/z: [M+Na] Calcd for C26
349.1598.
4-methoxy-5-phenylpentan-2-one (2h).15 This compound
3
+
2
O Si 349.1600; Found
was prepared according to the general procedure,
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Pd(PhCN)
2
Cl
2
(14.4 mg, 0.0375 mmol), purified by flash col-
4-oxobutyl benzoate (3c).19 This compound was prepared
according to the general procedure, purified by flash col-
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
umn chromatography (PE/EA = 10/1), as colorless oil (37.5
mg, 39%. H NMR (400 MHz, CDCl
H), 7.23 (d, J = 7.2 Hz, 1 H), 7.19 (d, J = 7.2 Hz, 2 H), 3.95-3.89
(m, 1 H), 3.34 (s, 3 H), 2.91 (dd, J = 13.6, 6.0 Hz, 1 H), 2.72
1
3
) δ 7.29 (t, J = 7.2 Hz, 2
umn chromatography (PE/EA = 10/1), yellow oil, 76.9 mg,
1
80%. H NMR (400 MHz, CDCl
3
) δ 9.84 (s, 1 H), 8.02 (d, J =
7.2 Hz, 2 H), 7.59-7.55 (m, 1 H), 7.47-7.43 (m, 2 H), 4.37 (t, J
(
(
dd, J = 13.6, 6.8 Hz, 1 H), 2.62 (dd, J = 16.4, 8.0 Hz, 1 H), 2.41
= 6.2 Hz, 2 H), 2.65 (t, J = 6.8 Hz, 2 H), 2.16-2.09 (m, 2 H).
13
1
13
1
dd, J = 16.0, 4.4 Hz, 1 H), 2.12 (s, 3 H). C{ H} NMR (100
) δ 207.7, 138.3, 129.8, 128.8, 126.7, 78.6, 57.7,
8.0, 40.1, 31.4.
-(3-oxobutyl) isoindoline-1,3-dione (2i).16 This com-
C{ H} NMR (100 MHz, CDCl
128.7, 64.2, 40.9, 21.8.
-oxopentyl benzoate (3d).20 This compound was pre-
3
) δ 201.5, 166.8, 133.4, 129.9,
MHz, CDCl
4
3
5
2
pared according to the general procedure, purified by flash
pound was prepared according to the general procedure,
purified by flash column chromatography (PE/EA = 10/1),
as a yellow solid (97.7 mg, 90%. H NMR (400 MHz, CDCl
δ 7.85-7.83 (m, 2 H), 7.73-7.70 (m, 2 H), 3.95 (t, J = 7.4 Hz,
column chromatography (PE/EA = 20/1), as colorless oil
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
(50.9 mg, 53%. H NMR (400 MHz, CDCl
3
) δ 9.80 (s, 1 H),
1
3
)
8.04-8.02 (m, 2 H), 7.58-7.54 (m, 1 H), 7.46-7.42 (m, 2 H),
4.34 (t, J = 5.6 Hz, 2 H), 2.54 (t, J = 5.8 Hz, 2 H), 1.82-1.81 (m,
1
3
1
4 H). 13C{
1
H} NMR (100 MHz, CDCl ) δ202.3, 166.9, 133.3,
2
H), 2.87 (t, J = 7.4 Hz, 2 H), 2.18 (s, 3 H). C{ H} NMR (100
MHz, CDCl ) δ 206.2, 168.4, 134.3, 132.4, 123.6, 41.9, 33.3,
0.3.
-(4-oxopentyl) isoindoline-1,3-dione (2j).17 This com-
3
130.6, 129.9, 128.7, 64.7, 43.7, 28.5, 19.0.
3
3
methyl 2-(3-chlorophenyl)-5-oxopentanoate (3e). This
compound was prepared according to the general proce-
2
pound was prepared according to the general procedure,
purified by flash column chromatography (PE/EA = 10/1),
as white solid (89 mg, 81%. H NMR (400 MHz, CDCl
dure, purified by flash column chromatography (PE/EA =
1
10/1), yellow oil, 94.2 mg, 78%. H NMR (400 MHz, CDCl
3
)
1
3
) δ
δ 9.74 (s, 1 H), 7.29-7.28 (m, 3 H), 7.18 (s, 1 H), 3.69 (s, 3 H),
7
.86-7.81 (m, 2 H), 7.73-7.69 (m, 2 H), 3.70 (t, J = 6.6 Hz, 2
3.61 (t, J = 7.6 Hz, 1 H), 2.45 (t, J = 7.0 Hz, 2 H), 2.40-2.35 (m,
13
1
H), 2.49 (t, J = 7.2 Hz, 2 H), 2.13 (s, 3 H), 1.94-1.91 (m, 2 H).
1 H), 2.15-2.08 (m, 1 H). C{ H} NMR (100 MHz, CDCl ) δ
3
13
1
C{ H} NMR (100 MHz, CDCl
123.5, 40.8, 37.4, 30.2, 22.9.
3
) δ 207.8, 168.8, 134.3, 132.3,
201.4, 173.7, 140.4, 135.0, 130.4, 128.4, 128.2, 126.5, 52.6,
+
50.2, 41.6, 25.8. HRMS (ESI-TOF) m/z: [M+Na] Calcd for
C
12
H
3
13ClO Na 263.0451; Found 263.0451.
-oxo-1-phenylbutyl acetate (3f).10a This compound was
4
General procedure for anti-Markovnikov Wacker oxi-
t
t
prepared according to the general procedure, purified by
dation under Pd- BuONO-O
Pd(PhCN) Cl (14.4 mg, 0.0375mmol) was weighed directly
into a 25 mL Schlenk tube and dried under high vacuum for
2
-system in
BuOH.
flash column chromatography (PE/EA = 10/1), as yellow oil
2
2
1
(97.1 mg, 94%. H NMR (400 MHz, CDCl
3
) δ 9.73 (s, 1 H),
7.37-7.31 (m, 5 H), 5.77 (t, J = 6.8 Hz, 1 H), 2.47 (t, J = 7.4 Hz,
2
0 mins. Under an atmosphere of oxygen (1 atm, balloon),
1
3
1
t
t
2 H), 2.27-2.12 (m, 2 H), 2.08 (s, 3 H). C{ H} NMR (100
MHz, CDCl ) δ 201.3, 170.5, 140.0, 128.9, 128.5, 126.6, 75.2,
0.2, 28.9, 21.4.
4-((tert-butyldiphenylsilyl)oxy)butanal (3g).10a This com-
BuOH (2 mL) and BuONO (10.3 mg, 0.1 mmol) were added
o
3
and stirred at 25 C. Alkene (0.5 mmol) was then added and
the resulting reaction mixture was monitored by TLC. After
completion, the reaction was quenched by addition of water
4
(
5 mL) and extracted three times with CH
bined organic layers were subsequently washed with brine
and dried over Na SO . The organic solvent was removed
2
Cl
2
. The com-
pound was prepared according to the general procedure,
purified by flash column chromatography (PE/EA = 40/1),
1
2
4
as yellow oil (93.2 mg, 57%. H NMR (400 MHz, CDCl
3
) δ
under reduced pressure then the crude mixture was exam-
9.79 (s, 1 H), 7.66-7.64 (m, 4 H), 7.45-7.37 (m, 6 H), 3.69 (t,
1
ined on H NMR spectrometer to determine the conversion
J = 6.0 Hz, 2 H), 2.55 (t, J = 7.2 Hz, 2 H), 1.92-1.86 (m, 2 H),
1
3
1
and selectivity using tert-butyl methyl ether (with nitrome-
thane as a dual standard) as internal standard. The crude
product was purified by chromatography on silica gel to af-
ford the corresponding products.
1.04 (s, 9 H) C{ H} NMR (100 MHz, CDCl
133.9, 130.0, 128.0, 63.2, 41.1, 27.1, 25.6, 19.4.
-methoxy-5-phenylpentanal (3h). This compound was
3
) δ 203.0, 135.9,
4
prepared according to the general procedure, purified by
4
-phenoxybutanal (3a).8a This compound was prepared
flash column chromatography (PE/EA = 20/1), as yellow oil
1
according to the general procedure, purified by flash col-
umn chromatography (PE/EA = 40/1), as yellow oil (66.9
(71.2 mg, 74%. H NMR (400 MHz, CDCl
3
) δ 9.72 (t, J = 1.6
Hz, 1 H), 7.32-7.28 (m, 2 H), 7.24-7.18 (m, 3 H), 3.41-3.35
(m, 1 H), 3.30 (s, 3 H), 2.93 (dd, J = 13.8, 5.8 Hz, 1 H), 2.67
(dd, J = 13.8, 6.8 Hz, 1 H), 2.48 (tt, J = 7.4, 1.6 Hz, 2 H), 1.88-
1
mg, 81%. H NMR (400 MHz, CDCl ) δ 9.86 (s, 1 H), 7.33 (t, J
3
= 7.8 Hz, 2 H), 6.97 (t, J = 7.4 Hz, 1 H), 6.90 (d, J = 8.0 Hz, 2
H), 4.02 (t, J = 5.8 Hz, 2 H), 2.69 (t, J = 7.0 Hz, 2 H), 2.18-2.11
(m, 2 H). C{ H} NMR (100 MHz, CDCl
129.8, 121.1, 114.7, 66.8, 40.9, 22.3.
5-phenoxypentanal (3b).18 This compound was prepared
according to the general procedure, purified by flash col-
13
1
1.80 (m, 1 H), 1.76-1.67 (m, 1 H). C{ H} NMR (100 MHz,
13
1
3
) δ 202.2, 158.9,
CDCl
3
) δ 202.3, 138.3, 129.4, 128.4, 126.3, 81.5, 57.0, 40.1,
+
40.0, 26.4. HRMS (ESI-TOF) m/z: [M+Na] Calcd for
C
12
H
16
2
O Na 215.1048; Found 215.4052.
2
1
4-(1, 3-dioxoisoindolin-2-yl)butanal (3i). This compound
umn chromatography (PE/EA = 40/1), as yellow oil (65.1
was prepared according to the general procedure, purified
1
mg, 73%. H NMR (400 MHz, CDCl
3
) δ 9.82 (s, 1 H), 7.32-7.28
by flash column chromatography (PE/EA = 10/1), as yellow
1
(
m, 2 H), 6.98-6.94 (m, 1 H), 6.91 (d, J = 8.0 Hz, 2 H), 3.99 (t,
oil (76.7 mg, 71%. H NMR (400 MHz, CDCl
3
) δ 9.77 (s, 1 H),
1
3
1
J = 5.6 Hz, 2 H), 2.55 (t, J = 6.0 Hz, 2 H), 1.85 (s, 4 H). C{ H}
NMR (100 MHz, CDCl ) δ 202.7, 159.2, 129.8, 121.0, 114.7,
7.5, 43.8, 29.0, 19.1.
7.87-7.83 (m, 2 H), 7.74-7.71 (m, 2 H), 3.74 (t, J = 6.8 Hz, 2
13
1
3
H), 2.54 (t, J = 6.8 Hz, 2 H), 2.05-1.98 (m, 2 H). C{ H} NMR
6
ACS Paragon Plus Environment

Page 5 of 7
The Journal of Organic Chemistry
(
100 MHz, CDCl
37.4, 21.5.
-(1, 3-dioxoisoindolin-2-yl) pentanal (3j).22 This com-
3
) δ 201.2, 168.7, 134.4, 132.3, 123.6, 41.4,
H), 5.93-5.83 (m, 1 H), 5.20-5.10 (m, 2 H), 4.38 (t, J = 6.6 Hz,
2 H), 2.56-2.51 (m, 2 H).
pent-4-en-1-yl benzoate (1d).27 This compound was pre-
1
2
3
4
5
6
7
8
9
5
pound was prepared according to the general procedure,
purified by flash column chromatography (PE/EA = 10/1),
as colorless oil (60.1 mg, 52%. H NMR (400 MHz, CDCl
9.76 (s, 1 H), 7.85-7.82 (m, 2 H), 7.73-7.70 (m, 2 H), 3.71 (t,
pared according to general procedure and purified by silica
1
gel column (PE/EA = 100/1). H NMR (400 MHz, CDCl ) δ
3
1
3
) δ
8.05 (d, J = 7.2 Hz, 2 H), 7.58-7.54 (m, 1 H), 7.46-7.42 (m, 2
H), 5.90-5.80 (m, 1 H), 5.10-5.00 (m, 2 H), 4.34 (t, J = 6.4 Hz,
2 H), 2.25-2.20 (m, 2 H), 1.91-1.84 (m, 2 H).
J = 6.6 Hz, 2 H), 2.50 (t, J = 6.6 Hz, 2 H), 1.77-1.65 (m, 4 H).
13
1
C{ H} NMR (100 MHz, CDCl
3
) δ 202.2, 168.8, 134.3, 132.4,
methyl 2-phenylpent-4-enoate (1e). This compound was
1
23.6, 43.5, 37.8, 28.3, 19.5.
28
prepared in 70% yield according to the literature method.
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
General procedures for homoallylation of phenols
and amines (1a, 1b, 1i, and 1j). To a solution of an aro-
matic alcohol or amine (10 mmol) and K CO (20 mmol) in
CH CN (30 mL) was added 4-bromo-1-butene (2.0 mL, 15
mmol), and the mixture was refluxed for 12 h. The reaction
mixture was concentrated, and the residue was partitioned
between CH
with CH Cl
were washed with water (2 × 10 mL), dried over anhydrous
Na SO , and concentrated in vacuo. The resulting residue
was purified by silica gel flash chromatography to provide
the titled compounds.
but-3-en-1-yloxy)benzene (1a).23 This compound was
prepared according to general procedure and purified by
silica gel column (PE/EA = 20/1). H NMR (400 MHz, CDCl )
δ 7.33-7.28 (m, 2 H), 6.99-6.97 (m, 1 H), 6.95-6.93 (m, 2 H),
6.00-5.89 (m, 1 H), 5.23-5.13 (m, 2 H), 4.05 (t, J = 6.8 Hz, 2
H), 2.58 (q, J = 6.8 Hz, 2 H).
H NMR (400 MHz, CDCl ): δ (ppm) 7.33-7.27 (m, 1 H), 7.26-
3
7.20(m, 3 H), 5.76-5.66 (m, 1 H), 5.11-5.02 (m, 2 H), 3.69 (s,
3 H), 3.64 (t, J = 7.6 Hz, 2 H), 2.86-2.79 (m. 1 H), 2.55-2.48
(m, 1 H).
2
3
3
1-phenylbut-3-en-1-yl acetate (1f). This compound was
prepared in 85% yield as a colorless oil according to the lit-
2
Cl
2
and water. The aqueous layer was extracted
10a 1
erature method.
H NMR (400 MHz, CDCl ) δ 7.36-7.25
3
2
2
(2 × 10 mL). The combined organic extracts
(
(
m, 5 H), 5.82-5.79 (m, 1 H), 5.75-5.65 (m, 1 H), 5.10-5.03
m, 2 H), 2.69-2.52 (m, 2 H), 2.07 (s, 3 H).
2
4
(
but-3-en-1-yloxy)(tert-butyl)diphenylsilane (1g). This
compound was prepared in 77% yield as a colorless oil ac-
2
5 1
cording to the literature method.
CDCl ) δ 7.68 (d, J = 6.4 Hz, 4 H), 7.45-7.37 (m, 6 H), 5.89-
.79 (m, 1 H), 5.08-5.01 (m, 2 H), 3.71 (t, J = 6.8 Hz, 2 H), 2.32
q, J = 6.8 Hz, 2 H), 1.05 (s, 9 H).
2-methoxypent-4-en-1-yl) benzene (1h). This compound
was prepared in 80% yield as a colorless oil according to the
H NMR (400 MHz,
(
3
5
(
1
3
(
1
0a 1
literature method.
H NMR (400 MHz, CDCl ) δ 7.30-7.26
3
(
pent-4-en-1-yloxy)benzene (1b).24 This compound was
(
m, 2 H), 7.23-7.20 (m, 3 H), 5.91-5.80 (m, 1 H), 5.10-5.06
prepared according to general procedure and purified by sil-
ica gel column (PE/EA = 20/1): 0.81 g, 50%, yellow oil. H
NMR (400 MHz, CDCl
(
m, 2 H), 3.48-3.42 (m, 1 H), 3.33 (s, 3 H), 2.83 (dd, J = 13.6,
1
6.4 Hz, 1 H), 2.74 (dd, J = 13.6, 6.0 Hz, 1 H), 2.31-2.18 (m, 2
3
) δ 7.27 (t, J = 7.6 Hz, 2 H), 6.95-6.89
H).
(
m, 3 H), 5.90-5.80 (m, 1 H), 5.08-4.99 (m, 2 H), 3.96 (t, J =
6
.4 Hz, 2 H), 2.24 (q, J = 7.2 Hz, 2 H), 1.92-1.85 (m, 2 H).
2-(but-3-en-1-yl)isoindoline-1,3-dione (1i).25 This com-
ASSOCIATED CONTENT
Supporting Information
pound was prepared according to general procedure and
1
The Supporting Information is available free of charge on
the ACS Publications website at DOI:
Procedure for screening reaction conditions and spectra of
products (PDF)
purified by silica gel column (PE/EA = 10/1). H NMR (400
MHz, CDCl ) δ 7.85-7.81 (m, 2 H), 7.72-7.68 (m, 2 H), 5.84-
.74 (m, 1 H), 5.08-5.00 (m, 2 H), 3.77 (t, J = 6.8 Hz, 2 H), 2.44
q, J = 6.8 Hz, 2 H).
-(pent-4-en-1-yl)isoindoline-1,3-dione (1j).23 This com-
3
5
(
2
AUTHOR INFORMATION
*ybkang@ustc.edu.cn
pound was prepared according to general procedure and
purified by silica gel column (PE/EA = 10/1). H NMR (400
MHz, CDCl
5
1
*ias_jpqu@njtech.edu.cn
3
) δ 7.86-7.82 (m, 2 H), 7.73-7.69 (m, 2 H), 5.87-
AUTHOR CONTIBUTION
§ K.-F.H. and X.-S. N. contributed equally to this work.
.77 (m, 1 H), 5.07-4.96 (m, 2 H), 3.70 (t, J = 7.2 Hz, 2 H), 2.12
q, J = 7.2 Hz, 2 H), 1.82-1.75 (m, 2 H).
(
General procedure for synthesis of starting materials
1c-1d). 4-Penten-1-ol (0.86 g, 10 mmol) and pyridine
0.95 g, 12mmol) were dissolved in 20 mL dry DCM. Benzoyl
ORCID
(
Yan-Biao Kang: 0000-0002-7537-4627
Jian-Ping Qu: 0000-0002-5002-5594
Notes
(
chloride (2.12 g, 12 mmol) was then added dropwise to the
o
solution at 0 C. The resulting reaction mixture was allowed
The authors declare no competing financial interest.
to warm up to rt and was stirred for 1 h. The insoluble salt
was filtered and the solvent was removed in vacuo. The res-
idue was purified by flash column chromatography(silica
gel, PE:EA = 100:1) to afford the titled product.
ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China
(
21602001, 21672196, U1463202), and the Fundamental Re-
search Funds for the Central Universities of China
WK2060190086) for financial support.
but-3-en-1-yl benzoate (1c).26 This compound was pre-
pared according to general procedure and purified by silica
gel column (PE/EA = 100/1). H NMR (400 MHz, CDCl
8.04 (d, J = 6.8 Hz, 2 H), 7.57-7.54 (m, 1 H), 7.46-7.42 (m, 2
(
1
3
) δ
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