One-pot sequential deoximation and allylation reactions of aldoximes in aqueous solution

Article abstract of DOI:10.1016/j.tet.2012.01.074

A simple procedure has been developed for conducting tin-mediated deoximation and allylation reactions of aldoximes in water to form homoallylic alcohols. Employing the new conditions, various homoallylic alcohols were produced in good to excellent yields

Full text of DOI:10.1016/j.tet.2012.01.074

Tetrahedron 68 (2012) 2630e2635
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One-pot sequential deoximation and allylation reactions of aldoximes in aqueous
solution
*
Mei-Huey Lin , Long-Zhi Lin, Tsung-Hsun Chuang, Han-Jun Liu
Department of Chemistry, National Changhua University of Education, Changhua 50007, Taiwan
a r t i c l e i n f o
a b s t r a c t
Article history:
A simple procedure has been developed for conducting tin-mediated deoximation and allylation re-
actions of aldoximes in water to form homoallylic alcohols. Employing the new conditions, various
homoallylic alcohols were produced in good to excellent yields.
Received 23 December 2011
Received in revised form 23 January 2012
Accepted 24 January 2012
Available online 30 January 2012
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Allylation
Deoximation
Aldoximes
Oximes
Homoallylic alcohols
1. Introduction
devised a procedure for carrying out aqueous, one-pot sequential
deoximation and allylation reactions of oximes that efficiently
As a consequence of the fact that it is readily available and en-
vironmentally benign, water has received considerable attention
recently as a solvent of choice for chemical reactions.1 In particular,
metal-mediated CeC bond forming reactions occurring in aqueous
media have been intensively investigated.2 Oximes are often used
in organic synthesis as protected forms of carbonyl compounds3 or
as carbonyl derivatives for purification and characterization pur-
poses.4 Aqueous Barbier conditions have recently been devised for
metal-mediated allylation reactions of oximes. However, owing to
the poor electrophilicity of oximes, only activated oximes partici-
pate in metal-mediated C]N bond allylation reactions in aqueous
media.5,6 In light of these limitations, one-pot sequential deoxi-
mation and allylation reactions in water have not been reported.
Oximes can be prepared from noncarbonyl compounds, such as
nitroalkanes7 or primary amines.8 In this regard, we have carried
out studies aimed at developing sequential deoximation and ally-
lation reactions of oximes in water. At the outset, we were cogni-
zant of the fact that regeneration of carbonyl compounds from
oximes classically involves the use of acid promoted hydrolysis or
related processes.9 In addition, in an earlier effort we demonstrated
that enol ethers serve as good substrates in tin-mediated allylation
reactions in water.10 In the investigation described below, we have
generate homoallylic alcohols. This one-pot deoximation and ally-
lation procedure that converts oximes to homoallylic alcohols
can serve as an alternative method for the synthesis of homoallylic
alcohols from nitroalkanes or primary amines via oximes
(Scheme 1).
R
R
NO2
or
NH2
OH R2
R1
ref 7, 8
R
NOH
R
Scheme 1. An alternative method for the synthesis of homoallylic alcohols from ni-
troalkanes or primary amines via oximes.
2. Results and discussion
In a previous study,10 we observed that formation of the allyl-
stannane intermediate by reaction of allyl bromide with tin in
water simultaneously creates sufficiently acidic conditions that
enable hydrolysis of enol ethers. We believed that the acidic con-
ditions that accompany generation of this intermediate in water
would be sufficient to promote deoximation reactions of oximes. In
order to probe this proposal, an investigation of tin-mediated one-
pot deoximation and allylation reactions of benzaldoxime with allyl
bromide was initiated. The results of this effort, in which various
precursors of in situ generated allylstannane were used, are pre-
sented in Table 1. The observations show that formation of the
* Corresponding author. Tel.: þ886 4 7232105x3543; fax: þ886 4 7211190; e-mail
address: mhlin@cc.ncue.edu.tw (M.-H. Lin).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.01.074

M.-H. Lin et al. / Tetrahedron 68 (2012) 2630e2635
2631
Table 1
homoallylic alcohol was formed exclusively in the Sn/TiCl3-medi-
ated deoximation and allylation reaction of benzaldoxime with 2b
(Table 3, entry 2). In addition, 2-halohomoallylic alcohols are gen-
erated in excellent yields in reactions of the halogenated allylic
Tin-mediated deoximation and allylation reactions of benzaldoxime in watera
OH
O
NOH
metal
H2O
Br
+
+
Ph
Ph
Ph
4
1a
2a
3a
bromides 2c and 2d (Table 3, entries 3, 4, 8, and 9). Finally, the g-
addition product 3p is formed predominantly with a high level of
diastereoselectivity in the reaction of benzaldoxime with crotyl
bromide (Table 3, entry 5). It is worth noting that a moderate level
Entry
Metal/additive (equiv)
Time (h)
3a
Yield (%)
1a/3a/4
1
2b
3
4
5
6
7
8
9
Sn (2.0)
Sn (2.0)/HBr
SnCl2 (2.0)
SnCl2 (1.8)/Kl (1.8)
SnCl2 (2.0)/Kl (2.0)/CuCl2 (1.0)
TiCl3 (1.0)
SnCl2 (2.0)/TiCl3 (1.0)
SnCl2 (2.0)/Kl (2.0)/TiCl3 (1.0)
Sn (2.0)/TiCl3 (1.0)
26
24
26
20
27
10
10
10
5
62
15:85:0
0:100:0
54:41:5
0:100:0
13:87:0
70:0:30
0:23:77
0:100:0
0:100:0
of diastereoselectivity in the
the Sn-mediated allylation reaction of benzaldehyde and crotyl
halide has been reported.10c,13 Moreover, the
-addition product 3p
is formed predominantly with moderate level of diaster-
g-addition product 3p prepared from
95
NAc
94
g
NAc
NAc
NAc
91
a
eoselectivity in the Sn/TiCl3-mediated allylation reaction of benz-
aldehyde with crotyl bromide (83% yield, syn/anti¼1.48:1).
93
3. Conclusion
a
Conditions: 1a (1.0 mmol), allyl bromide 2a (2.0 mmol), and indicated metal in
water (2.0 mL) at rt.
b
In summary, the study described above has led to a one-pot
deoximation and allylation reaction of aldoximes in water. The re-
action is simple, mild, and inexpensive. In addition, this process
serves as an alternative method for the synthesis of homoallylic
alcohols from aldoximes.
Conditions: 1a (1.0 mmol), allyl bromide (2.0 mmol), tin powder (2.0 mmol),
and HBr (0.2 mL) in water (1.8 mL) at rt.
c
Not isolated.
allylstannane intermediate in water by reaction of allyl bromide
with tin appears to promote the formation of conditions needed to
deoximate benzaldoxime (Table 1, entry 1). The overall rate of this
process was found to be accelerated when aqueous HBr was pres-
ent in the aqueous solution (Table 1, entry 2).11 In addition, the
allylstannane intermediate generated from SnCl2 was not as ef-
fective as that generated from tin (Table 1, entry 1 vs entry 3).
Gratifyingly, this SnCl2-mediated one-pot deoximation and allyla-
tion reactions of benzaldoxime was boosted with an additive KI
(Table 1, entry 4).10
The reduction of oximes to form imines, using trivalent titanium
reductant has been described.12 Thus, we envisaged that imines
formed in this manner would be susceptible to rapid hydrolysis to
produce aldehydes, which would readily react with the allyltin
intermediate (Table 1, entry 1 vs 9 and entry 3 vs 7). The in-
tervention and effect of this reduction process are seen by com-
paring the rates of reactions promoted by using SnCl2/KI/TiCl3
versus Sn/TiCl3 (Table 1, entry 8 vs 9). In addition, it has been re-
ported that regeneration of carbonyl compounds from oximes can
be induced by cupric chloride under hydrolytic conditions.9 How-
ever, the observations (Table 1, entry 4 vs 5) show that the SnCl2/KI-
mediated deoximation and allylation reaction of benzaldoxime is
retarded by the presence of cupric chloride. As can be seen by
viewing the combined results displayed in Table 1, Sn/TiCl3 serves
as a superior reagent combination for carrying out one-pot se-
quential deoximation and allylation reactions of benzaldoxime in
water.
By using the conditions described above, the aldoxime sub-
strate scope of the deoximation and allylation reaction with allyl
bromide was probed (Table 2).11 As can be seen by viewing the
results displayed in Table 2, the yields of these processes, starting
with both aromatic (Table 2, entries 1e10) and long chain ali-
phatic (Table 2, entries 11 and 12) oximes, are good to excellent.
Interestingly, the presence of a free phenol group, that is, present
in 1i and the presence of a free hydroxy group, that is, present in
1l do not alter the efficiency of the reaction (Table 2, entries 9
and 12).
Deoximation and allylation reactions of benzaldoxime with
other allylic halides were explored next (Table 3). These processes
give rise to various homoallylic alcohols in good to excellent yields.
Interestingly, lactone formation occurred when the allylic bromide
2b was employed in the Sn/TiCl3-mediated allylation reaction of
aliphatic aldoxime (Table 3, entry 7). However, the corresponding
4. Experimental section
4.1. General
All commercially available chemicals were used without fur-
ther purification. Oximes 1ael were prepared according to the
reported procedures.14 Iodoallylic bromides 2d was prepared from
reported procedure.10 TLC analyses were run on a glass plate
(Silica-gel 60 F254) and were visualized using UV or a solution of
phosphomolybdic acid in ethanol (5 wt %) or p-anisaldehyde
stain. Flash chromatography was performed using silica-gel
(70e230 mesh). 1H and 13C NMR spectra were recorded on
a 300 MHz spectrometer. Chemical shifts are reported relative to
CHCl3 [dH 7.24, dC (central line) 77.0]. Mass spectra and high-
resolution mass spectra were recorded under electron spray in-
terface (ESI) conditions.
4.2. Synthesis
4.2.1. General procedure for allylation reactions of aldoximes in an
aqueous solution to form homoallylic alcohols. SnCl2/KI condition: A
mixture of aldoxime 1 (1.0 mmol), an allylating agent (2.0 mmol),
tin chloride dihydrate (1.8 mmol), and potassium iodide (1.8 mmol)
in THF/H2O (1/3, 2 mL) was stirred at ambient temperature. Re-
action was monitored by TLC until no starting material was ob-
served. The mixture was extracted with Et2O or CH2Cl2 (3ꢀ5 mL).
The combined organic layers were washed with 5% Na2S2O3(aq)
(10 mL), dried over Na2SO4, and concentrated in vacuo. The residue
was subjected to silica-gel chromatography to furnish the pure
product 2 (Et2O/hexanes (1:5)). Sn/TiCl3 condition: A mixture of
aldoxime 1 (1.0 mmol), an allylating agent (2.0 mmol), tin
(1.5 mmol), and TiCl3 (1.0 mmol, 20% in 3% hydrochloric acid) in
THF/H2O (1/3, 2 mL) was stirred at ambient temperature. Reaction
was monitored by TLC until no starting material was observed. The
mixture was extracted with Et2O or CH2Cl2 (3ꢀ5 mL). The com-
bined organic layers were dried over Na2SO4 and concentrated in
vacuo. The residue was subjected to silica-gel chromatography to
furnish the pure product 2 (Et2O/hexanes (1:5)).
4.2.1.1. 1-Phenylbut-3-en-1-ol (3a). Following the general pro-
cedure, the title compound was obtained (138 mg, 93%). Oil; TLC
(Et2O/hexanes (1:2)) Rf¼0.35; 1H NMR (300 MHz, CDCl3)
d 2.05 (br
s, 1H), 2.47e2.53 (m, 2H), 4.72 (dd, J¼7.5, 5.4 Hz, 1H), 5.11e5.19 (m,

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M.-H. Lin et al. / Tetrahedron 68 (2012) 2630e2635
Table 2
Tin-mediated deoximation and allylation reactions of aldoximesa
SnCl2/KI
or
OH
N
OH
Br
2a
+
R
R
Sn/TiCl3
3
1
H2O/THF
Entry
1
Substrate
Product
Yielda (%)
94
Yieldb (%)
93
OH
1a
1b
NOH
3a
3b
OH
OH
2
3
4
5
97
95
NAc
NAc
NOH
NOH
1c
1d
1e
3c
3d
OH
OH
92
96
NAc
94
NOH
NOH
3e
Cl
Cl
OH
NOH
1f
6
94
93
3f
Br
Br
OH
OH
NC
NC
7
8
1g
1h
NOH
NOH
86
96
88
91
3g
3h
MeO
MeO
MeO
MeO
OMe
OMe
OH
NOH
Br
1i
66
80
92
83
3i
9
Br
OH
OH
OH
OH
3j
1j
NOH
10
11
HON
OH
C8H17
1k
81
91
91
C8H17
3k
NOH
NOH
OH
2
NAc
12
HO
HO
1l
3l
a
Conditions: oxime (1.0 mmol), allyl bromide (2.0 mmol), and SnCl2 (1.8 mmol)/KI (1.8 mmol).
Conditions: oxime (1.0 mmol), allyl bromide (2.0 mmol), and Sn (1.5 mmol)/TiCl3 (1.0 mmol).
Reaction was not performed.
b
c

M.-H. Lin et al. / Tetrahedron 68 (2012) 2630e2635
2633
Table 3
Tin-mediated deoximation and allylation reactions of aldoxime with various allylic bromidesa
Entry
Substrate
Allylating agent
Product
Yielda
(%)
Yieldb
(%)
OH
1
2
3
4
1a
1a
1a
1a
Br
94
80
93
3a
2a
Ph
Ph
Ph
Ph
OH CO2Et
OH Br
CO2Et
95
3m
2b
Br
Br
c
92
91
NA
90
Br
2c
3n
3o
OH I
I
Br
2d
OH
OH
94
(3.7:1)
88
(3.3:1)
5
1a
Br
d
d
2e
3p
Ph
6
7
8
1k
1k
Br
2a
81
91
82
3k
3q
C8H17
O
O
C8H17
CO2Et
NAc
Br
2b
OH I
I
NAc
NAc
76
3r
1k
1l
Br
C8H17
HO
2d
OH I
2
I
81e
9
3s
Br
2d
a
Conditions: oxime (1.0 mmol), allylic bromide (2.0 mmol), and SnCl2 (1.8 mmol)/KI (1.8 mmol) in water (2.0 mL) at rt.
Conditions: oxime (1.0 mmol), allylic bromide (2.0 mmol), and Sn (2.0 mmol)/TiCl3 (1.0 mmol) in water (2.0 mL) at rt.
Reaction was not performed.
b
c
d
e
Diastereomeric ratio¼(syn/anti).
The product was isolated as the corresponding acetate derivative.
2H), 5.70e5.84 (m, 1H), 7.25e7.35 (m, 5H); 13C NMR (75 MHz,
CDCl3)
134.2 (C), 134.8 (CH), 136.7 (C), 138.9 (C); MS m/z (rel intensity) 176
(Mþ, 1), 158 (11), 143 (22), 135 (100); HRMS [M]þ for C12H16O:
176.1201, found 176.1194.
d
43.8 (CH2), 73.3 (CH), 118.5 (CH2), 125.8 (CH ꢀ2), 127.5
(CH), 128.4 (CH ꢀ2), 134.4 (CH), 143.8 (C). These data are in
agreement with those reported in the literature.15
4.2.1.4. 1-(4-Ethylphenyl)but-3-en-1-ol
(3d). Following the
4.2.1.2. 1-p-Tolylbut-3-en-1-ol (3b). Following the general pro-
general procedure, the title compound was obtained (162 mg, 92%).
cedure, the title compound was obtained (157 mg, 97%). Oil; TLC
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.38; IR (neat): 3387, 2968,
(Et2O/hexanes (1:2)) Rf¼0.30; 1H NMR (300 MHz, CDCl3)
d
2.03 (d,
1435 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d
1.23 (t, J¼7.8 Hz, 3H), 2.13
J¼2.1 Hz, 1H), 2.33 (s, 3H), 2.50 (dd, J¼6.9, 6.9 Hz, 2H), 4.69 (br t,
(d, J¼3.0 Hz, 1H), 2.50 (dd, J¼6.9, 6.9 Hz, 2H), 2.62 (q, J¼7.8 Hz, 2H),
4.66e4.71 (m, 1H), 5.11e5.18 (m, 2H), 5.73e5.87 (m, 1H), 7.17 (d,
J¼8.1 Hz, 2H), 7.26 (d, J¼8.1 Hz, 2H); 13C NMR (75 MHz, CDCl3)
J¼6.9 Hz, 1H), 5.10e5.17 (m, 2H), 5.68e5.83 (m, 1H), 7.13e7.16 (d,
J¼8.1 Hz, 2H), 7.24 (d, J¼8.1 Hz, 2H); 13C NMR (75 MHz, CDCl3)
d 21.0
(CH3), 43.7 (CH2), 73.1 (CH), 118.2 (CH2), 125.7 (CH ꢀ2), 129.1 (CH
ꢀ2), 134.6 (CH), 137.2 (C), 140.9 (C). These data are in agreement
with those reported in the literature.16
d 15.5 (CH3), 28.5 (CH2), 43.7 (CH2), 73.2 (CH), 118.2 (CH2), 125.8 (CH
ꢀ2), 127.8 (CH ꢀ2), 134.6 (CH), 141.1 (C), 143.5 (C). These data are in
agreement with those reported in the literature.17
4.2.1.3. 1-(2,4-Dimethylphenyl)but-3-en-1-ol (3c). Following the
general procedure, the title compound was obtained (167 mg, 95%).
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.45; IR (neat): 3377, 2925, 1632,
4.2.1.5. 1-(4-Chlorophenyl)but-3-en-1-ol (3e). Following the
general procedure, the title compound was obtained (172 mg, 94%).
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.28; 1H NMR (300 MHz, CDCl3)
1446 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d
2.10 (br s, 1H), 2.30 (s, 3H),
d
2.14 (d, J¼2.7 Hz, 1H), 2.35e2.55 (m, 2H), 4.67e4.72 (m, 1H),
2.31 (s, 3H), 2.35e2.55 (m, 2H), 4.92 (q, J¼4.8 Hz, 1H), 5.15e5.21 (m,
5.11e5.17 (m, 2H), 5.71e5.80 (m, 1H), 7.20e7.31 (m, 4H); 13C NMR
(75 MHz, CDCl3)
2H), 5.78e5.90 (m, 1H), 6.79 (m, 1H), 7.04 (d, J¼7.8 Hz, 1H), 7.36 (d,
d
43.8 (CH2), 72.5 (CH), 118.8 (CH2), 127.2 (CH ꢀ2),
J¼7.8 Hz, 1H); 13C NMR (75 MHz, CDCl3)
d
18.9 (CH3), 20.9 (CH3),
128.5 (CH ꢀ2), 133.1 (C), 133.9 (CH), 142.3 (C). These data are in
42.6 (CH2), 69.5 (CH), 118.0 (CH2), 125.1 (CH), 126.8 (CH), 131.0 (CH),
agreement with those reported in the literature.18

2634
M.-H. Lin et al. / Tetrahedron 68 (2012) 2630e2635
4.2.1.6. 1-(4-Bromophenyl)but-3-en-1-ol (3f). Following the
d
1.41e1.63 (m, 6H), 1.70e1.90 (m, 2H), 2.08e2.32 (m, 2H), 3.63 (t,
general procedure, the title compound was obtained (211 mg, 93%).
J¼6.0 Hz, 3H), 5.10 (d, J¼12.6 Hz, 2H), 5.73e5.87 (m, 1H). These data
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.28; IR (neat): 3327, 2910, 1489,
are in agreement with those reported in the literature.10
1412 cmꢁ1
;
1H NMR (300 MHz, CDCl3)
d
2.09 (d, J¼3.0 Hz, 1H),
2.41e2.51 (m, 2H), 4.66e4.71 (m, 1H), 5.11e5.18 (m, 2H), 5.69e5.83
4.2.1.13. Ethyl 4-hydroxy-2-methylene-4-phenylbutanoate
(m, 1H), 7.20 (d, J¼7.8 Hz, 2H), 7.45 (d, J¼7.8 Hz, 2H); 13C NMR
(3m). Following the general procedure, the title compound was
(75 MHz, CDCl3)
d
43.8 (CH2), 72.5 (CH), 118.9 (CH2), 121.2 (C), 127.5
obtained (209 mg, 95%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.20; 1
H
(CH ꢀ2), 131.5 (CH ꢀ2), 133.9 (CH), 142.8 (C). These data are in
NMR (300 MHz, CDCl3)
d
1.29 (t, J¼7.2 Hz, 3H), 2.61e2.80 (m, 3H),
agreement with those reported in the literature.18
4.19 (q, J¼7.2 Hz, 2H), 4.86 (dd, J¼8.4, 3.9 Hz, 1H), 5.70 (d, J¼1.5 Hz,
1H), 6.21 (d, J¼1.5 Hz, 1H), 7.24e7.36 (m, 5H); 13C NMR (75 MHz,
4.2.1.7. 3-(1-Hydroxybut-3-enyl)benzonitrile (3g). Following the
general procedure, the title compound was obtained (152 mg, 88%).
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.10; 1H NMR (300 MHz, CDCl3)
CDCl3) d 14.1 (CH3), 42.5 (CH2), 61.0 (CH2), 73.1 (CH), 125.7 (CH
ꢀ2), 127.4 (CH), 128.1 (CH2), 128.3 (CH ꢀ2), 137.1 (C), 143.9 (C),
167.7 (C). These data are in agreement with those reported in the
literature.23
d
2.26 (d, J¼2.7 Hz, 1H), 2.37e2.56 (m, 2H), 4.73e4.78 (m, 1H),
5.12e5.18 (m, 2H), 5.68e5.82 (m, 1H), 7.40e7.56 (m, 3H), 7.58 (d,
J¼1.2 Hz, 1H); 13C NMR (75 MHz, CDCl3)
d
43.8 (CH2), 72.1 (CH),
4.2.1.14. 3-Bromo-1-phenylbut-3-en-1-ol (3n). Following the
general procedure, the title compound was obtained (209 mg, 92%).
Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.30; IR (neat): 3389, 3040, 2914,
112.4 (C), 118.8 (C), 119.5 (CH2), 129.1 (CH), 129.4 (CH), 130.3 (CH),
131.1 (CH), 133.3 (CH), 145.3 (C). These data are in agreement with
those reported in the literature.19
1628 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d 2.33 (br s, 1H), 2.69e2.86
(m, 2H), 4.98e5.02 (m, 1H), 5.10 (d, J¼1.8 Hz, 1H), 5.65 (d, J¼1.8 Hz,
4.2.1.8. 1-(3,5-Dimethoxyphenyl)but-3-en-1-ol (3h). Following
the general procedure, the title compound was obtained (190 mg,
91%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.18; IR (neat): 3400, 3080,
1H), 7.24e7.38 (m, 5H); 13C NMR (75 MHz, CDCl3)
d
51.2 (CH2), 71.5
(CH),119.9 (CH2),125.7 (CH ꢀ2),127.8 (CH),128.5 (CH ꢀ2),130.0 (C),
142.8 (C). These data are in agreement with those reported in the
literature.18
2930, 1607 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d
2.14 (d, J¼2.7 Hz, 1H),
2.44e2.52 (m, 2H), 3.77 (s, 6H), 4.64 (t, J¼7.2 Hz, 1H), 5.10e5.18 (m,
2H), 5.72e5.86 (m, 1H), 6.35 (d, J¼2.4 Hz, 1H), 6.49 (d, J¼2.4 Hz,
4.2.1.15. 3-Iodo-1-phenylbut-3-en-1-ol (3o). Following the gen-
eral procedure, the title compound was obtained (247 mg, 90%). Oil;
TLC (Et2O/hexanes (1:2)) Rf¼0.48; IR (neat): 3378, 3031, 2899,
2H); 13C NMR (75 MHz, CDCl3)
(CH), 99.4 (CH), 103.7 (CH ꢀ2), 118.3 (CH2), 134.4 (CH), 146.5 (C),
160.8 (C ꢀ2). These data are in agreement with those reported in
the literature.20
d
43.6 (CH2), 55.3 (CH3 ꢀ2), 73.3
1615 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d
2.22 (d, J¼3.0 Hz, 1H), 2.73
(d, J¼6.9 Hz, 2H), 4.92e4.97 (m, 1H), 5.82 (d, J¼1.2 Hz, 1H), 6.12 (d,
J¼1.2 Hz, 1H), 7.24e7.38 (m, 5H); 13C NMR (75 MHz, CDCl3)
d 54.7
4.2.1.9. 2-Bromo-3-(1-hydroxybut-3-enyl)-6-methoxyphenol
(3i). Following the general procedure, the title compound was
obtained (251 mg, 92%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.18; IR
(CH2), 72.3 (CH), 106.9 (C), 125.9 (CH ꢀ2), 127.8 (CH), 128.5 (CH ꢀ2),
127.9 (CH2), 142.6 (C); MS m/z (rel intensity) 274 (Mþ, 2), 127 (7),
107 (100), 79 (62); HRMS [M]þ for C10H11IO: 273.9855, found
273.9862.
(neat): 3456, 2937, 1609, 1488 cmꢁ1 1H NMR (300 MHz, CDCl3)
;
d
2.28 (br s, 1H), 2.31e2.38 (m, 1H), 2.55e2.63 (m, 1H), 3.88 (s, 3H),
5.02e5.06 (m, 1H), 5.12e5.19 (m, 2H), 5.78e5.92 (m, 1H), 6.01 (br s,
4.2.1.16. 2-Methyl-1-phenylbut-3-en-1-ol (3p, anti/syn: 1:3.7).
Following the general procedure, the title compound was obtained
(152 mg, 94%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.40; IR (neat):
1H), 6.83 (d, J¼8.1 Hz, 1H), 7.04 (d, J¼8.1 Hz, 1H); 13C NMR (75 MHz,
CDCl3) d 42.1 (CH2), 56.3 (CH3), 71.5 (CH), 108.3 (C), 109.6 (CH), 117.6
(CH), 118.4 (CH2), 134.4 (CH), 135.7 (C), 142.7 (C), 146.2 (C); MS m/z
(rel intensity) 272 (Mþ, 4), 257 (11), 255 (12), 231 (100); HRMS [M]þ
for C11H13BrO3: 272.0048, found 272.0041.
3412, 2926, 1634, 1447 cmꢁ1; 1H NMR (300 MHz, CDCl3)
d 0.85 (d,
J¼6.9 Hz, 0.6H), 0.99 (d, J¼6.9 Hz, 2.4H), 1.98 (d, J¼3.3 Hz, 0.8H),
2.20 (d, J¼3.3 Hz, 0.2H), 2.40e2.60 (m, 1H), 4.30e4.40 (m, 0.2H),
4.58e4.61 (m, 0.8H), 5.00e5.07 (m, 1.6H), 5.10e5.20 (m, 0.4H),
5.69e5.80 (m, 1H), 7.23e7.35 (m, 5H); 13C NMR (75 MHz, CDCl3)
4.2.1.10. 1,10-(1,4-Phenylene)dibut-3-en-1-ol (3j). Following the
general procedure, the title compound was obtained (181 mg,
83%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.10; IR (neat): 3366, 2910,
d
14.0, 16.5, 44.6, 46.3, 77.4, 77.8, 115.5, 116.8, 126.5, 126.8, 127.3,
127.6, 128.0, 128.2, 140.3, 140.6, 152.5. These data are in agreement
with those reported in the literature.24
1643, 1421 cmꢁ1 1H NMR (300 MHz, CDCl3)
; d 2.30 (br s, 2H),
2.44e2.49 (m, 4H), 4.68 (q, J¼7.2 Hz, 2H), 5.09e5.15 (m, 4H),
5.69e5.83 (m, 2H), 7.29 (br s, 4H); 13C NMR (75 MHz, CDCl3)
d
43.7
4.2.1.17. 3-Methylene-5-octyldihydrofuran-2(3H)-one
(3q).
(CH2 ꢀ2), 73.0 (CH ꢀ2), 118.3 (CH2 ꢀ2), 125.8 (CH ꢀ4), 134.4 (CH
ꢀ2), 143.1 (C ꢀ2). These data are in agreement with those reported
in the literature.21
Following the general procedure, the title compound was obtained
(172 mg, 82%). Oil; TLC (Et2O/hexanes (1:2)) Rf¼0.55; 1H NMR
(300 MHz, CDCl3)
d
0.80 (t, J¼6.0 Hz, 3H), 1.37e1.72 (m, 14H),
2.51e2.59 (m, 1H), 2.98e3.06 (m, 1H), 4.46e4.51 (m, 1H), 5.59 (d,
J¼2.4 Hz, 1H), 6.19 (d, J¼2.4 Hz, 1H). These data are in agreement
with those reported in the literature.25
4.2.1.11. Dodec-1-en-4-ol (3k). Following the general procedure,
the title compound was obtained (168 mg, 91%). Oil; TLC (Et2O/
hexanes (1:2)) Rf¼0.38; 1H NMR (300 MHz, CDCl3)
d 0.85 (t,
J¼6.9 Hz, 3H), 1.15e1.50 (m, 14H), 1.70 (t, J¼3.6 Hz, 1H), 2.05e2.15
(m, 1H), 2.22e2.30 (m, 1H), 3.61 (br s, 1H), 5.07e5.11 (m, 2H),
4.2.1.18. 2-Iodododec-1-en-4-ol (3r). Following the general
procedure, the title compound was obtained (220 mg, 71%). Oil; TLC
(Et2O/hexanes (1:2)) Rf¼0.68; IR (neat): 2928, 2856, 1739,
5.73e5.87 (m, 1H); 13C NMR (75 MHz, CDCl3)
d 14.0 (CH3), 22.6
(CH2), 25.6 (CH2), 29.2 (CH2), 29.5 (CH2), 29.6 (CH2), 31.8 (CH2), 36.8
(CH2), 41.9 (CH2), 70.7 (CH), 117.9 (CH2), 134.9 (CH). These data are
in agreement with those reported in the literature.22
1233 cmꢁ1
;
1H NMR (300 MHz, CDCl3)
d
0.85 (t, J¼6.6 Hz, 3H),
1.25e1.50 (m,14H),1.73 (br s,1H), 2.36e2.56 (m, 2H), 3.75e3.86 (m,
1H), 5.81 (d, J¼1.2 Hz, 1H), 6.13 (q, J¼1.2 Hz, 1H); 13C NMR (75 MHz,
CDCl3)
d 14.1 (CH3), 22.6 (CH2), 25.6 (CH2), 29.2 (CH2), 29.5 (CH2),
4.2.1.12. Oct-7-ene-1,5-diol (3l). Following the general pro-
cedure, the title compound was obtained (131 mg, 91%). Oil; TLC
(EtOAc/hexanes (1:2)) Rf¼0.08; 1H NMR (300 MHz, CDCl3)
29.6 (CH2), 31.8 (CH2), 36.1 (CH2), 52.9 (CH2), 69.8 (CH), 107.9 (C),
128.5 (CH2); MS m/z (rel intensity) 310 (Mþ,1),168 (34),143 (48), 69
(100); HRMS [M]þ for C12H23IO: 310.0794, found 310.0797.

M.-H. Lin et al. / Tetrahedron 68 (2012) 2630e2635
2635
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Picher, M. T.; Arroyo, P.; Sez, J. A. J. Org. Chem. 2006, 71, 9319; (c) Czekelius, C.;
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4.2.1.19. 7-Iodooct-7-ene-1,5-diyl diacetate (3s). Following the
general procedure, the crude diol was then treated with Ac2O
(2 mmol) and pyridine (2 mmol) in Et2O (5 mL) at rt overnight to
give the title compound (287 mg, 81%). An oil; TLC (EtOAc/hexanes
(1:4)) Rf¼0.47; 1H NMR (300 MHz, CDCl3)
d 1.28e1.39 (m, 2H),
1.52e1.65 (m, 4H), 1.99 (s, 6H), 2.53 (dd, J¼14.7, 5.4 Hz, 1H), 2.66
(dd, J¼14.7, 7.5 Hz, 1H), 4.00 (t, J¼6.6 Hz, 2H), 5.03e5.11 (m, 1H),
5.74 (s, 1H), 6.04 (s, 1H); 13C NMR (75 MHz, CDCl3)
d 20.9 (CH3), 21.0
(CH3), 21.5 (CH2), 28.2 (CH2), 32.8 (CH2), 49.4 (CH2), 64.0 (CH2), 71.9
(CH), 104.9 (C), 128.3 (CH2), 170.3 (C), 171.0 (C). These data are in
agreement with those reported in the literature.10
8. Suzuki, K.; Watanabe, T.; Murahashi, S.-I. Angew. Chem., Int. Ed. 2008, 47,
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9. Quan, N.; Shi, X.-X.; Nie, L.-D.; Dong, J.; Zhu, R.-H. Synlett 2011, 1028.
10. Lin, M.-H.; Hung, S.-F.; Lin, L.-Z.; Tsai, W.-S.; Chuang, T.-H. Org. Lett. 2011, 13, 332
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D. E.; Smith, L. L.; Gross, P. H.; Samoshin, V. V. Green Chem. 2002, 4, 317; (b)
Samoshin, V. V.; Gremyachinskiy, D. E.; Smith, L. L.; Bliznets, I. V.; Gross, P. H.
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J. Chem. Soc., Perkin Trans. 1 1997, 1629.
11. The Sn/HBr reaction condition was not pursued further because its
high acidity that might alter the functional group compatibility of the
process.
Acknowledgements
Financial support from the National Science Council of the Re-
public of China, Taiwan (NSC100-2113-M-018-004-MY2) is grate-
fully acknowledged.
12. (a) Lee, S. Y.; Lee, B. S.; Lee, C.-W.; Oh, D. Y. J. Org. Chem. 2000, 65, 256; (b)
Timms, G. H.; Wildsmith, E. Tetrahedron Lett. 1971, 2, 195.
Supplementary data
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Tetrahedron: Asymmetry 1996, 7, 1535.
Supplementary data related to this article can be found online at
doi:10.1016/j.tet.2012.01.074.
ꢀ
ꢀ
14. Ramon, R. S.; Bosson, J.; Díez-Gonzalez, S.; Marion, N.; Nolan, S. P. J. Org. Chem.
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