An efficient approach to 2-bromoalken-3-ols by regioselective bromohydroxylation reaction of simple allenes with NBS

Article abstract of DOI:10.1002/ejoc.201001676

A regioselective bromohydroxylation reaction of simple allenes affording 2-bromoalken-3-ols in moderate-to-good yields has been developed by using NBS as the electrophilic reagent in a mixture of 1,4-dioxane/H₂O (1:1) at room temperature. Throu

Full text of DOI:10.1002/ejoc.201001676

FULL PAPER
DOI: 10.1002/ejoc.201001676
An Efficient Approach to 2-Bromoalken-3-ols by Regioselective
Bromohydroxylation Reaction of Simple Allenes with NBS
Wangqing Kong,[a] Binjie Guo,[a] Chunling Fu,[a] and Shengming Ma*[a]
Keywords: Allenes / Bromine / Electrophilic addition / Regioselectivity / Bromohydroxylation
A regioselective bromohydroxylation reaction of simple all-
enes affording 2-bromoalken-3-ols in moderate-to-good
yields has been developed by using NBS as the electrophilic
reagent in a mixture of 1,4-dioxane/H2O (1:1) at room tem-
perature. Through this study it has been concluded that the
regioselectivity is determined by various factors including
steric and electronic effects of the substituents of the allene
moiety.
ents on the allenes. In this paper we report our recent re-
sults on the regioselective halohydroxylation reactions of
simple allenes.
Introduction
Halohydroxylations of carbon–carbon double bonds are
one of the most important methods for providing 2-halo-
substituted alcohols[1] as two functional groups, that is, X
and OH, are introduced into the substrates in one synthetic
operation. During the last 10 years we have developed
highly regio- and stereoselective halohydroxylation (X = Cl,
Br, I) reactions of allenyl sulfoxides,[2a,2b] sulfones,[2c] phos-
phane oxides,[2d,2e] sulfides,[3a,3b] selenides,[3c] and fur-
anones.[4] The reactions of sulfoxides, sulfones, and phos-
phane oxides afforded (E) products, whereas those of sul-
fides, selenides, and furanones afforded (Z) products.[5]
Note that such reactions of simple allenes are usually
nonselective, affording a mixture of products: The addition
of chlorine to allenes to afford an almost equimolar mixture
of 2,3-dichloropropene and propargyl chloride in moderate
overall yields (approximately 50%) has been reported by
Peer,[6] whereas the addition of hydrogen bromide to propa-
1,2-diene produced the cyclodimerization products, cis- and
trans-1,3-dibromo-1,3-dimethylcyclobutane, as well as the
conventional adducts 2-bromopropene and 2,2-dibro-
mopropane.[7] The reactions of sulfenyl chlorides with
propa-1,2-diene yielded primary monoadducts (allyl chlo-
rides), diadducts, vinyl chlorides (by rearrangement of the
monoadducts), and 1,2-dichloropropanes (by hydrochlori-
nation of the monoadducts).[8] This phenomenon can be
attributed to the fact that the regio- and stereoselectivity of
this reaction are strongly influenced by the nature of the
electrophile and steric and electronic effects of the substitu-
Results and Discussion
First we used CH3CN/H2O (10:1), which is the most
commonly used solvent[5] in the halohydroxylation of 4-
phenyl-1,2-butadiene. However, the reaction afforded a
mixture of regioisomeric products, 3-bromo-1-phenyl-3-
buten-2-ol (2a) and (Z)-2-bromo-4-phenyl-2-buten-1-ol (Z)-
3a [2a/(Z)-3a = 82:18] in 17% combined yield with the re-
covery of 20% of 4-phenyl-1,2-butadiene (1a; Entry 1,
Table 1). Then a series of solvents, including 1,4-dioxane,
CH3NO2, and CH2Cl2, were tested; 1,4-dioxane was found
to be the best (Entries 1–4, Table 1). We studied the effect
of the ratio of 1,4-dioxane/water and found that 1,4-diox-
ane/H2O (1:1) gave the best results (Entries 2 and 5–8,
Table 1). With 1.5 equiv. of NBS, the yield dropped unex-
pectedly (Entry 9, Table 1). Note that the reaction of 1a
with bromine afforded 2a and (Z)-3a in 57% combined
yield with a selectivity of 68:32 (Entry 11, Table 1). Finally,
we defined the best reaction conditions for the bromo-
hydroxylation of simple allenes to give 2-bromoalken-3-ols:
NBS (1.0 equiv.) in 1,4-dixoane/H2O (1:1) at room tempera-
ture (Entry 10, Table 1). Note that the bromohydroxylation
reaction occurred at the more substituted C=C bond with
the bromine atom adding to the central carbon atom of
the allene. Thus, the regioselectivity is determined by the
electronic effects (not the steric effect) of these two C=C
bonds.
The results of the bromohydroxylation of different simple
allenes with NBS under these standard reaction conditions
are summarized in Table 2. Note that the monosubstituted
allenes 1 reacted with NBS to afford 2-bromoalken-3-ols 2
in good yields with good selectivity towards the more sub-
stituted C=C bonds: R1 may be benzyl (Entry 1, Table 2),
[a] Laboratory of Molecular Recognition and Synthesis, Depart-
ment of Chemistry, Zhejiang University,
Hangzhou 310027, Zhejiang, P. R. China
Fax: +86-216-260-9305
E-mail: masm@sioc.ac.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201001676.
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2-Bromoalken-3-ols by Bromohydroxylation
Table 1. Optimization of the reaction conditions for the bromohydroxylation reaction of 4-phenyl-1,2-butadiene (1a).[a]
Entry X (Quantity [equiv.])
Solvent
t [h] Combined yield of 2a + (Z)-3a [%] 2a/(Z)-3a[b] Recovery of 1a [%][b]
[b]
1
2
3
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.2)
NBS (1.5)
NBS (1.0)
Br2 (1.0)
CH3CN/H2O (10:1) 10.5
dioxane/H2O (10:1) 10.5
CH3NO2/H2O (10:1) 10.5
17
39
–
82:18
87:13
–
63:37
89:11
60:40
90:10
50:50
91:9
20
27
50
24
0
41
10
0
4
CH2Cl2/H2O (10:1)
dioxane/H2O (1:1)
dioxane
dioxane/H2O(1:10)
H2O
dioxane/H2O (1:1)
dioxane/H2O(1:1)
dioxane/H2O(1:1)
17
11.5
10
18
0.5
10
24
64
20
61
20
45
71
57
5[c]
6
7
8
9
10
11
0
0
0
13
0.8
92:8
68:32
1
[a] All reactions used 0.3 mmol of 1a unless otherwise noted. [b] Determined by H NMR by using CH2Br2 as the internal standard. [c]
0.6 mmol 1a was used.
Table 2. Bromohydroxylation reaction of simple allenes with NBS.
Entry
1
t [h]
NMR yield of 2 + 3 [%] (2/3)[a]
Isolated yield of 2 [%]
Isolated yield of 3 [%]
R1
R2
1
2
3
4
5
6
7
8
Bn
H (1a)
H (1b)
H (1c)
H (1d)
H (1e)
H (1f)
H (1g)
Ph (1h)
Ph (1i)
Ph (1j)
Ph (1k)
16
17
19
22
16
17
16
23
17.5
20
72 (91:9)
86 (94:6)
74 (96:4)
90 (94:6)
85 (93:7)
65 (89:11)
74 (78:22)
76 (88:12)
89 (85:15)
76 (87:13)
76 (88:12)
63 (2a)
68 (2b)
62 (2c)
82 (2d)
69 (2e)
58 (2f)
59 (2g)
65 (2h)
63 (2i)
64 (2j)
60 (2k)
4 [(Z)-3a]
5 [(Z)-3b]
5 [(Z)-3c]
5 [(Z)-3d]
4 [(Z)-3e]
3 [(Z)-3f]
9 [(Z)-3g]
8 [(E)-3h]
11 [(E)-3i]
10 [(E)-3j]
7 [(E)-3k]
n-C10H21
n-C8H17
n-C7H15
n-C6H13
c-C6H11
Ph
Et
9
10
11
n-C4H9
n-C6H13
allyl
12
1
[a] Combined yields of 2 and 3 were determined by H NMR spectroscopy using CH2Br2 as the internal standard. The ratios of 2/3 are
given in parentheses.
normal alkyl (Entries 2–5, Table 2), cyclic alkyl (Entry 6, sulting in a more electrophilic attack at the terminal C=C
Table 2), or phenyl (Entry 7, Table 2). Even with geminally double bond (Scheme 1). These two products may also be
disubstituted substrates, when R1 is an alkyl group and R2 easily separated by chromatography on silica gel.
is a phenyl group, the corresponding products were afforded
in satisfactory yields and relatively high selectivities (En-
tries 8–10, Table 2). With R1 being an allyl group, no reac-
tion occurred at the allylic C=C bond. Note that products
2 and (Z)-3 may be separated easily by chromatography on
silica gel, and the byproduct (Z)-3 is formed with a single
configuration, as determined by an NOE study (see the
Supporting Information).
Scheme 1.
The substrates with both R1 and R2 as alkyl or phenyl
groups led to a low regioselectivity, probably due to the
With trisubstituted substrate 1n, due to the influence of
increased steric effect of the coexistence of R1 and R2 re- the two phenyl substituents, regioisomer 3n with the hy-
Eur. J. Org. Chem. 2011, 2278–2285
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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W. Kong, B. Guo, C. Fu, S. Ma
FULL PAPER
Scheme 2.
droxy group at the less hindered terminal is the main prod- moalken-3-ols formed, this reaction may be useful in or-
uct, which indicates that the regioselectivity is a combina- ganic synthesis. The regioselectivity of the reaction is deter-
tion of electronic and steric effects (Scheme 2). Note that mined by electronic effects or in some cases by a combina-
pure (Z)-2n, as determined by an NOE study (see the Sup- tion of electronic and steric effects. Further studies on the
porting Information), can be obtained in 51% isolated yield synthetic applications of this reaction are being conducted
by highly selective elimination of (E)-2n to give 1,1-di- in our laboratory.
phenylbut-2-yn-1-ol (4n) using TBAF[9] (Scheme 2).
2-Bromoalken-3-ols are very useful building blocks in or-
ganic synthesis and can be exploited for the fast introduc-
tion of molecular complexity. The synthetic potential of this
methodology was demonstrated by the reactions of 2a
(Scheme 3). By coupling protocols of the C–Br bond in 2a,
1-alkynyl, aryl, and styryl groups can be introduced into
the 2-position.[10] Elimination of HBr from 2a afforded pro-
pargylic alcohol 4a.[9]
Experimental Section
General: 1H and 13C NMR spectra were recorded with a Bruker
AM 300 MHz. IR spectra were recorded with a Perkin–Elmer
983G instrument. Elemental analyses were recorded with a Carlo-
Erba EA1110 elementary analysis instrument. Mass spectrometry
was performed with an HP 5989A system. High-resolution mass
spectrometry was determined with a Finnigan MAT 8430 or
Bruker APEXIII instrument. Unless otherwise indicated, chemicals
and solvents were purchased from commercial suppliers.
Synthesis of 2-Bromoalk-2-enols: The 1,2-allenes used in this study
were prepared according to a reported procedure.[11]
3-Bromo-1-phenyl-3-buten-2-ol (2a) and (Z)-2-Bromo-4-phenyl-2-
buten-1-ol [(Z)-3a]. Typical Procedure: NBS (1780.2 mg,
10.0 mmol) and H2O (20 mL) were sequentially added to a solution
of buta-2,3-dienylbenzene (1a; 1300.4 mg, 10.0 mmol) in dioxane
(20 mL). After stirring at room temp. for 16 h, the reaction was
complete, as monitored by TLC. The mixture was then quenched
with a saturated aqueous solution of Na2S2O3 (20 mL), and then
water (50 mL) was added. This mixture was extracted with diethyl
ether (3ϫ30 mL), washed with a saturated aqueous solution of
NaCl (3ϫ20 mL), and dried with anhydrous Na2SO4. After fil-
tration and concentration, the NMR yield of 2a was 65% and the
ratio of 2a/(Z)-3a was 91:9, as determined by 1H NMR analysis
using CH2Br2 as the internal standard. Chromatography on silica
gel (petroleum ether/ethyl acetate, 10:1) of the crude product af-
forded 2a (1416.6 mg, 63%) and (Z)-3a (93.0 mg, 4%).
1
2a: Liquid. H NMR (300 MHz, CDCl3): δ = 7.38–7.20 (m, 5 H,
ArH), 5.76 (dd, J = 2.1 and 0.9 Hz, 1 H, =CH), 5.53 (d, J = 1.8 Hz,
1 H, =CH), 4.33 (q, J = 6.3 Hz, 1 H, CHO), 3.06 (dd, J = 13.7
and 5.6 Hz, 1 H, one proton in ArCH2), 2.90 (dd, J = 13.7 and
7.4 Hz, 1 H, one proton in ArCH2), 2.12–2.02 (m, 1 H, OH) ppm.
13C NMR (75 MHz, CDCl3): δ = 136.7, 135.8, 129.5, 128.5, 126.8,
Scheme 3.
117.6, 76.9, 41.8 ppm. IR (neat): ν = 3396, 3062, 3028, 2924, 1625,
˜
Conclusions
1603, 1496, 1454, 1383, 1257, 1187, 1127, 1076, 1053, 1026 cm–1.
MS (70 eV, EI): m/z (%) = 147 (11.35) [M – Br]+, 91 (100).
C10H11BrO (226.00): calcd. C 52.89, H 4.88; found C 52.91, H 4.94.
We have developed a convenient method for the efficient
synthesis of 2-bromo-substituted allylic alcohols by the re-
gioselective bromohydroxylation of simple allenes with
NBS. Owing to the ready availability of the starting all-
1
(Z)-3a: Liquid. H NMR (300 MHz, CDCl3): δ = 7.35–7.15 (m, 5
H, ArH), 6.17 (tt, J = 7.1 and 1.1 Hz, 1 H, =CH), 4.24 (d, J =
enes[11] and NBS, as well as the potential of the 2-bro- 5.7 Hz, 2 H, CH2O), 3.55 (d, J = 6.9 Hz, 2 H, ArCH2), 2.36 (t, J
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2-Bromoalken-3-ols by Bromohydroxylation
= 6.2 Hz, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ = 138.7,
H2O]+, 95 (100). HRMS: calcd. for C11H2179BrO [M]+ 248.0776;
found 248.0768.
128.8, 128.6, 128.4, 127.2, 126.4, 68.2, 37.0 ppm. IR (neat): ν =
˜
3363, 3062, 3027, 2917, 2861, 1655, 1602, 1495, 1453, 1263, 1201,
1095, 1010 cm–1. MS (70 eV, EI): m/z (%) = 228 (3.67) [M(81Br)]+,
226 (3.77) [M(79Br)]+, 129 (100). HRMS: calcd. for C10H1179BrO
[M]+ 225.9993; found 225.9989.
2-Bromo-1-decen-3-ol (2d) and (Z)-2-Bromo-2-decen-1-ol [(Z)-3d]:
The reaction of deca-1,2-diene (1d; 276.1 mg, 2.0 mmol) and NBS
(358.3 mg, 2.0 mmol) in 1,4-dioxane (7.0 mL) and H2O (7.0 mL) at
room temp. for 22 h afforded 2d (385.8 mg, 82%) and (Z)-3d
(25.3 mg, 5%) (petroleum ether/ethyl acetate, 50:1 Ǟ 30:1 Ǟ 20:1).
The following compounds 2b–2n and 3b–3n were prepared accord-
ing to this procedure.
1
The ratio of 2d/(Z)-3d was 94:6 as determined by H NMR spec-
troscopy using CH2Br2 as the internal standard.
2-Bromo-1-tridecen-3-ol (2b) and (Z)-2-Bromo-2-tridecen-1-ol [(Z)-
3b]: The reaction of trideca-1,2-diene (1b; 900.9 mg, 5.0 mmol) and
NBS (895.6 mg, 5.0 mmol) in 1,4-dioxane (10.0 mL) and H2O
(10.0 mL) at room temp. for 17 h afforded 2b (963.2 mg, 68%) and
(Z)-3b (61.8 mg, 5%) (petroleum ether/ethyl acetate, 50:1 Ǟ 40:1
Ǟ 30:1 Ǟ 20:1 Ǟ 10:1). The ratio of 2b/(Z)-3b was 94:6, as deter-
mined by 1H NMR spectroscopy using CH2Br2 as the internal stan-
dard.
2d: Liquid. 1H NMR (300 MHz, CDCl3): δ = 5.86 (dd, J = 2.0 and
0.8 Hz, 1 H, =CH), 5.54 (d, J = 1.8 Hz, 1 H, =CH), 4.07 (q, J =
6.2 Hz, 1 H, CHO), 2.16–2.00 (m, 1 H, OH), 1.73–1.50 (m, 2 H,
CH2), 1.42–1.13 (m, 10 H, 5 CH2), 0.87 (t, J = 6.8 Hz, 3 H, CH3)
ppm. 13C NMR (75 MHz, CDCl3): δ = 137.6, 116.9, 76.0, 35.2,
31.7, 29.3, 29.2, 25.2, 22.6, 14.1 ppm. IR (neat): ν = 3373, 2955,
˜
2926, 2856, 1627, 1465, 1414, 1379, 1164, 1104, 1054 cm–1. MS
(70 eV, EI): m/z (%) = 155 (10.90) [M – Br]+, 57 (100). C10H19BrO
(234.06): calcd. C 51.07, H 8.14; found C 51.18, H 8.13.
1
2b: Liquid. H NMR (300 MHz, CDCl3): δ = 5.86 (d, J = 1.5 Hz,
1 H, =CH), 5.55 (d, J = 1.8 Hz, 1 H, =CH), 4.07 (q, J = 6.3 Hz, 1
H, CHO), 1.98 (d, J = 5.7 Hz, 1 H, OH), 1.75–1.50 (m, 2 H, CH2),
1.41–1.12 (m, 16 H, 8 CH2), 0.87 (t, J = 6.6 Hz, 3 H, CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 137.6, 116.9, 76.1, 35.3, 31.9,
(Z)-3d:[12] Liquid. 1H NMR (300 MHz, CDCl3): δ = 6.00 (t, J =
6.9 Hz, 1 H, =CH), 4.24 (d, J = 5.4 Hz, 2 H, CH2O), 2.19 (q, J =
7.2 Hz, 2 H, CH2), 2.07 (br. s, 1 H, OH), 1.50–1.18 (m, 10 H, 5
CH2), 0.89 (t, J = 6.8 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 130.6, 126.5, 68.5, 31.8, 30.8, 29.15, 29.07, 28.2, 22.6,
29.6, 29.54, 29.49, 29.3, 25.2, 22.7, 14.1 ppm. IR (neat): ν = 3354,
˜
2924, 2854, 1627, 1466, 1378, 1309, 1162, 1073 cm–1. MS (70 eV,
EI): m/z (%) = 197 (11.67) [M – Br]+, 136 (100). C13H25BrO
(276.11): calcd. C 56.32, H 9.09; found C 56.33, H 8.93.
14.1 ppm. IR (neat): ν = 3345, 2925, 2857, 1659, 1459 1377, 1281,
˜
1221, 1134, 1091, 1017 cm–1. MS (70 eV, EI): m/z (%) = 236 (5.10)
[M(81Br)]+, 234 (5.17) [M(79Br)]+, 137 (27.93) [M – Br – H2O]+, 81
(100).
(Z)-3b: Liquid. 1H NMR (300 MHz, CDCl3): δ = 6.00 (t, J =
7.1 Hz, 1 H, =CH), 4.24 (s, 2 H, CH2O), 2.29 (br. s, 1 H, OH),
2.19 (q, J = 7.1 Hz, 2 H, CH2), 1.50–1.20 (m, 16 H, 8 CH2), 0.88
(t, J = 6.8 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
130.6, 126.4, 68.4, 31.9, 30.8, 29.6, 29.5, 29.4, 29.3, 29.2, 28.2, 22.7,
2-Bromo-1-nonen-3-ol (2e) and (Z)-2-Bromo-2-nonen-1-ol [(Z)-3e]:
The reaction of nona-1,2-diene (1e; 621.0 mg, 5.0 mmol) and NBS
(895.3 mg, 5.0 mmol) in 1,4-dioxane (10.0 mL) and H2O (10.0 mL)
at room temp. for 16 h afforded 2e (766.5 mg, 69%) and (Z)-3e
(44.9 mg, 4%) (petroleum ether/ethyl acetate, 50:1 Ǟ 40:1 Ǟ 30:1
Ǟ 20:1). The ratio of 2e/(Z)-3e was 93:7 as determined by 1H NMR
spectroscopy using CH2Br2 as the internal standard.
14.1 ppm. IR (neat): ν = 3334, 2925, 2854, 1657, 1462, 1377, 1296,
˜
1221, 1131, 1093, 1011 cm–1. MS (70 eV, EI): m/z (%) = 278 (3.04)
[M(81Br)]+, 276 (2.96) [M(79Br)]+, 197 (2.44) [M – Br]+, 179 (15.50)
[M – Br – H2O]+, 95 (100). HRMS: calcd. for C13H2579BrO [M]+
276.1089; found 276.1084.
1
2e: Liquid. H NMR (300 MHz, CDCl3): δ = 5.84 (d, J = 1.2 Hz,
1 H, =CH), 5.52 (d, J = 1.8 Hz, 1 H, =CH), 4.05 (t, J = 6.5 Hz, 1
H, CHO), 2.44 (br. s, 1 H, OH), 1.75–1.43 (m, 2 H, CH2), 1.41–
1.12 (m, 8 H, 4 CH2), 0.86 (t, J = 6.3 Hz, 3 H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 137.5, 116.8, 76.0, 35.1, 31.6, 28.9,
2-Bromo-1-undecen-3-ol (2c) and (Z)-2-Bromo-2-undecen-1-ol [(Z)-
3c]: The reaction of undeca-1,2-diene (1c; 760.1 mg, 5.0 mmol) and
NBS (895.6 mg, 5.0 mmol) in 1,4-dioxane (10.0 mL) and H2O
(10.0 mL) at room temp. for 19 h afforded 2c (772.1 mg, 62%) and
(Z)-3c (58.6 mg, 5%) (petroleum ether/ethyl acetate, 50:1 Ǟ 40:1
Ǟ 30:1 Ǟ 20:1 Ǟ 10:1). The ratio of 2c/(Z)-3c was 96:4 as deter-
mined by 1H NMR spectroscopy using CH2Br2 as the internal stan-
dard.
25.1, 22.5, 14.0 ppm. IR (neat): ν = 3373, 2961, 2927, 2858, 1626,
˜
1466, 1379, 1160, 1098, 1065, 1046 cm–1. MS (70 eV, EI): m/z (%)
= 123 (85.22) [M – Br – H2O]+, 43 (100). C9H17BrO (220.05): calcd.
C 48.88, H 7.75; found C 48.93, H 7.80.
(Z)-3e:[13] Liquid. 1H NMR (300 MHz, CDCl3): δ = 6.00 (t, J =
7.1 Hz, 1 H, =CH), 4.24 (s, 2 H, CH2O), 2.19 (q, J = 7.2 Hz, 2 H,
CH2), 2.08 (br. s, 1 H, OH), 1.50–1.15 (m, 8 H, 4 CH2), 0.89 (t, J
= 6.8 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 130.6,
1
2c: Liquid. H NMR (300 MHz, CDCl3): δ = 5.85 (d, J = 0.9 Hz,
1 H, =CH), 5.53 (d, J = 1.5 Hz, 1 H, =CH), 4.06 (t, J = 6.5 Hz, 1
H, CHO), 2.27 (br. s, 1 H, OH), 1.80–1.45 (m, 2 H, CH2), 1.41–
1.12 (m, 12 H, 6 CH2), 0.86 (t, J = 6.6 Hz, 3 H, CH3) ppm. 13C
NMR (75 MHz, CDCl3): δ = 137.5, 116.9, 76.0, 35.2, 31.8, 29.4,
126.5, 68.5, 31.6, 30.8, 28.8, 28.2, 22.5, 14.1 ppm. IR (neat): ν =
˜
3329, 2956, 2926, 2857, 1651, 1459, 1374, 1134, 1092, 1015 cm–1.
MS (70 eV, EI): m/z (%) = 222 (3.01) [M(81Br)]+, 220 (3.43)
[M(79Br)]+, 123 (26.22) [M – Br – H2O]+, 43 (100).
29.3, 29.2, 25.1, 22.6, 14.1 ppm. IR (neat): ν = 3357, 2925, 2856,
˜
1628, 1465, 1379, 1305, 1069 cm–1. MS (70 eV, EI): m/z (%) = 169
(10.64) [M – Br]+, 41 (100). C11H21BrO (248.08): calcd. C 53.02, H
8.49; found C 53.10, H 8.47.
2-Bromo-1-cyclohexyl-2-propen-1-ol (2f) and (Z)-2-Bromo-3-cyclo-
hexyl-2-propen-1-ol [(Z)-3f]: The reaction of propa-1,2-dienylcy-
clohexane (1f; 611.1 mg, 5.0 mmol) and NBS (895.5 mg, 5.0 mmol)
in 1,4-dioxane (10.0 mL) and H2O (10.0 mL) at room temp. for
17 h afforded 2f (632.3 mg, 58%) and (Z)-3f (31.1 mg, 3%) (petro-
leum ether/ethyl acetate, 50:1 Ǟ 40:1 Ǟ 30:1 Ǟ 20:1 Ǟ 15:1). The
ratio of 2f/(Z)-3f was 89:11 as determined by 1H NMR spec-
troscopy using CH2Br2 as the internal standard.
(Z)-3c: Liquid. 1H NMR (300 MHz, CDCl3): δ = 6.00 (t, J =
6.9 Hz, 1 H, =CH), 4.24 (s, 2 H, CH2O), 2.19 (q, J = 7.1 Hz, 2 H,
CH2), 2.11 (br. s, 1 H, OH), 1.45–1.18 (m, 12 H, 6 CH2), 0.88 (t,
J = 6.6 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
130.6, 126.4, 68.5, 31.8, 30.8, 29.4, 29.20, 29.19, 28.2, 22.6,
14.1 ppm. IR (neat): ν = 3333, 2925, 2855, 1657, 1461, 1377, 1292,
˜
1263, 1221, 1131, 1092, 1014 cm–1. MS (70 eV, EI): m/z (%) = 250
2f: Liquid. H NMR (300 MHz, CDCl3): δ = 5.82–5.77 (m, 1 H,
1
(4.88) [M(81Br)]+, 248 (5.07) [M(79Br)]+, 151 (16.64) [M – Br –
=CH), 5.55 (d, J = 1.8 Hz, 1 H, =CH), 3.70 (t, J = 7.1 Hz, 1 H,
Eur. J. Org. Chem. 2011, 2278–2285
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2281

W. Kong, B. Guo, C. Fu, S. Ma
FULL PAPER
CHO), 2.11 (d, J = 6.6 Hz, 1 H, CH), 1.96 (d, J = 12.9 Hz, 1 H,
OH), 1.82–1.45 (m, 5 H, one proton in CH2 and 2 CH2), 1.35–0.80
(m, 5 H, one proton in CH2 and 2 CH2) ppm. 13C NMR (75 MHz,
CDCl3): δ = 136.5, 118.0, 80.6, 40.9, 29.3, 27.9, 26.2, 25.8,
(%) = 242 (8.33) [M(81Br)]+, 240 (8.53) [M(79Br)]+, 211 (100).
HRMS: calcd. for C11H1381BrO [M]+ 242.0129; found 242.0129.
1
(E)-3h: Liquid. H NMR (300 MHz, CDCl3): δ = 7.42–7.24 (m, 3
H, ArH), 7.20–7.08 (m, 2 H, ArH), 4.13 (d, J = 6.3 Hz, 2 H,
CH2O), 2.62 (q, J = 7.5 Hz, 2 H, CH2), 1.98 (br. s, 1 H, OH), 0.95
(t, J = 7.7 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
145.5, 139.3, 128.4, 128.0, 127.6, 124.2, 65.6, 32.3, 11.3 ppm. IR
25.7 ppm. IR (neat): ν = 3385, 2926, 2852, 1626, 1450, 1384, 1309,
˜
1261, 1209, 1191, 1156, 1081, 1054, 1028 cm–1. MS (70 eV, EI): m/z
(%) = 220 (0.85) [M(81Br)]+, 218 (0.90) [M(79Br)]+, 83 (100).
C9H15BrO (218.03): calcd. C 49.33, H 6.90; found C 49.28, H 6.88.
(neat): ν = 3386, 3058, 3024, 2970, 2930, 2873, 1621, 1491, 1443,
˜
(Z)-3f: Liquid. 1H NMR (300 MHz, CDCl3): δ = 5.83 (d, J = 1375, 1239, 1200, 1113, 1086, 1057, 1010 cm–1. MS (70 eV, EI): m/z
8.7 Hz, 1 H, =CH), 4.22 (d, J = 4.2 Hz, 2 H, CH2O), 2.50–2.30 (m, (%) = 242 (43.11) [M(81Br)]+, 240 (43.88) [M(79Br)]+, 161 (58.19)
1 H, CH), 2.09 (br. s, 1 H, OH), 1.80–1.58 (m, 5 H, one proton in [M – Br]+, 143 (100) [M – Br – H2O]+. HRMS: calcd. for
CH2 and 2 CH2), 1.40–1.00 (m, 5 H, one proton in CH2 and 2
C11H1379BrO [M]+ 240.0150; found 240.0142.
CH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 135.6, 124.5, 68.5,
2-Bromo-3-phenyl-1-hepten-3-ol (2i) and (E)-2-Bromo-3-phenyl-2-
hepten-1-ol [(E)-3i]: The reaction of hepta-1,2-dien-3-ylbenzene (1i;
861.1 mg, 5.0 mmol) and NBS (895.1 mg, 5.0 mmol) in 1,4-dioxane
(10.0 mL) and H2O (10.0 mL) at room temp. for 17.5 h afforded 2i
(845.4 mg, 63%) and (E)-3i (151.8 mg, 11%) (petroleum ether/ethyl
acetate, 40:1 Ǟ 30:1 Ǟ 20:1). The ratio of 2i/(E)-3i was 85:15 as
determined by 1H NMR spectroscopy using CH2Br2 as the internal
standard.
39.9, 31.6, 25.9, 25.5 ppm. IR (neat): ν = 3332, 2925, 2851, 1654,
˜
1448, 1314, 1276, 1215, 1146, 1081, 1005 cm–1. MS (70 eV, EI): m/z
(%) = 220 (1.57) [M(81Br)]+, 218 (1.56) [M(79Br)]+, 121 (25.87) [M –
Br – H2O]+, 99 (100). HRMS: calcd. for C9H1579BrO [M]+
218.0306; found 218.0313.
2-Bromo-1-phenyl-2-propen-1-ol (2g) and (Z)-2-Bromo-3-phenyl-2-
propen-1-ol [(Z)-3g]: The reaction of propa-1,2-dienylbenzene (1g;
232.2 mg, 2.0 mmol) and NBS (358.4 mg, 2.0 mmol) in 1,4-dioxane
(7.0 mL) and H2O (7.0 mL) at room temp. for 16 h afforded 2g
(251.3 mg, 59%) and (Z)-3g (39.2 mg, 9%) (petroleum ether/diethyl
ether, 10:1 Ǟ 8:1). The ratio of 2g/(Z)-3g was 78:22 as determined
2i: Liquid. 1H NMR (300 MHz, CDCl3): δ = 7.48–7.41 (m, 2 H,
ArH), 7.40–7.24 (m, 3 H, ArH), 6.04 (d, J = 2.1 Hz, 1 H, =CH),
5.71 (d, J = 2.4 Hz, 1 H, =CH), 2.45 (s, 1 H, OH), 2.23–2.10 (m,
1 H, one proton in CH2), 2.08–1.93 (m, 1 H, one proton in CH2),
1.50–1.02 (m, 4 H, 2 CH2), 0.87 (t, J = 7.4 Hz, 3 H, CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 143.1, 141.0, 128.1, 127.5, 125.6,
1
by H NMR spectroscopy using CH2Br2 as the internal standard.
1
2g: Liquid. H NMR (300 MHz, CDCl3): δ = 7.50–7.30 (m, 5 H,
ArH), 6.05 (dd, J = 1.7 and 1.1 Hz, 1 H, =CH), 5.69 (d, J = 1.8 Hz,
1 H, =CH), 5.26 (s, 1 H, CHO), 2.61 (br. s, 1 H, OH) ppm. 13C
NMR (75 MHz, CDCl3): δ = 139.6, 135.5, 128.5, 128.3, 126.6,
117.2, 79.8, 39.1, 25.8, 23.0, 14.0 ppm. IR (neat): ν = 3556, 3473,
˜
3088, 3060, 3028, 2957, 2931, 2871, 1621, 1494, 1467, 1447, 1378,
1323, 1258, 1127, 1090, 1051, 1033 cm–1. MS (70 eV, EI): m/z (%) =
270 (4.14) [M(81Br)]+, 268 (4.25) [M(79Br)]+, 211 (100). C13H17BrO
117.6, 77.8 ppm. IR (neat): ν = 3378, 3063, 3031, 2880, 1625, 1494,
˜
1454, 1387, 1233, 1193, 1151, 1113, 1079, 1034, 1024 cm–1. MS (268.05): calcd. C 58.01, H 6.37; found C 58.09, H 6.64.
(70 eV, EI): m/z (%) = 214 (37.73) [M(81Br)]+, 212 (38.35)
1
(E)-3i: Liquid. H NMR (300 MHz, CDCl3): δ = 7.38–7.24 (m, 3
[M(79Br)]+, 107 (100). HRMS: calcd. for C9H979BrO [M]+
H, ArH), 7.18–7.11 (m, 2 H, ArH), 4.12 (d, J = 6.0 Hz, 2 H,
211.9837; found 211.9834.
CH2O), 2.65–2.50 (m, 2 H, =CCH2), 2.13 (br. s, 1 H, OH), 1.40–
(Z)-3g:[14] Liquid. H NMR (300 MHz, CDCl3): δ = 7.69–7.59 (m,
1.20 (m, 4 H, 2 CH2), 0.86 (t, J = 6.9 Hz, 3 H, CH3) ppm. 13C
1
2 H, ArH), 7.45–7.30 (m, 3 H, ArH), 7.10 (s, 1 H, =CH), 4.42 (d, NMR (75 MHz, CDCl3): δ = 144.4, 139.6, 128.4, 128.0, 127.5,
J = 3.6 Hz, 2 H, CH2O), 3.30 (br. s, 1 H, OH) ppm. 13C NMR
124.8, 65.6, 38.7, 28.9, 22.4, 13.8 ppm. IR (neat): ν = 3403, 3058,
(75 MHz, CDCl3): δ = 134.8, 128.9, 128.1, 128.0, 127.6, 125.1, 3024, 2956, 2937, 2865, 1626, 1490, 1451, 1381, 1228, 1128, 1069,
˜
69.1 ppm. IR (neat): ν = 3333, 3056, 3025, 2917, 2859, 1647, 1603,
1009 cm–1. MS (70 eV, EI): m/z (%) = 270 (19.21) [M(81Br)]+, 268
(20.41) [M(79Br)]+, 189 (26.98) [M – Br]+, 171 (18.26) [M – Br –
H2O]+, 129 (100). HRMS: calcd. for C13H1779BrO [M]+ 268.0463;
found 268.0458.
˜
1491, 1446, 1367, 1285, 1089, 1071 cm–1. MS (70 eV, EI): m/z (%)
= 214 (29.75) [M(81Br)]+, 212 (29.70) [M(79Br)]+, 133 (100) [M –
Br]+. HRMS: calcd. for C9H979BrO [M]+ 211.9837; found
211.9836.
2-Bromo-3-phenyl-1-nonen-3-ol (2j) and (E)-2-Bromo-3-phenyl-2-
nonen-1-ol [(E)-3j]: The reaction of nona-1,2-dien-3-ylbenzene (1j;
399.0 mg, 2.0 mmol) and NBS (358.2 mg, 2.0 mmol) in 1,4-dioxane
(7.0 mL) and H2O (7.0 mL) at room temp. for 20 h afforded 2j
(376.1 mg, 64%) and (E)-3j (60.1 mg, 10%) (petroleum ether/ethyl
acetate, 40:1 Ǟ 30:1 Ǟ 20:1). The ratio of 2j/(E)-3j was 87:13 as
determined by 1H NMR spectroscopy using CH2Br2 as the internal
standard.
2-Bromo-3-phenyl-1-penten-3-ol (2h) and (E)-2-Bromo-3-phenyl-2-
penten-1-ol [(E)-3h]: The reaction of penta-1,2-dien-3-ylbenzene
(1h; 288.0 mg, 2.0 mmol) and NBS (358.4 mg, 2.0 mmol) in 1,4-
dioxane (7.0 mL) and H2O (7.0 mL) at room temp. for 23 h af-
forded 2h (311.9 mg, 65%) and (E)-3h (39.3 mg, 8%) [eluent: first
time, petroleum ether/ethyl acetate, 40:1 Ǟ 30:1 Ǟ 20:1; after this
separation, (E)-3h was not pure; second time, petroleum ether/ethyl
acetate, 30:1 Ǟ 20:1 gave pure (E)-3h]. The ratio of 2h/(E)-3h was
88:12 as determined by 1H NMR spectroscopy using CH2Br2 as
the internal standard.
2j: Liquid. 1H NMR (300 MHz, CDCl3): δ = 7.44–7.34 (m, 2 H,
ArH), 7.33–7.18 (m, 3 H, ArH), 5.97 (d, J = 2.7 Hz, 1 H, =CH),
5.64 (d, J = 2.7 Hz, 1 H, =CH), 2.35 (s, 1 H, OH), 2.16–2.02 (m,
1 H, one proton in CH2CO), 2.00–1.86 (m, 1 H, one proton in
CH2CO), 1.45–1.28 (m, 1 H, one proton in CH2), 1.26–0.96 (m, 7
1
2h: Liquid. H NMR (300 MHz, CDCl3): δ = 7.42–7.33 (m, 2 H,
ArH), 7.32–7.14 (m, 3 H, ArH), 5.95 (d, J = 2.4 Hz, 1 H, =CH),
5.63 (d, J = 2.4 Hz, 1 H, =CH), 2.38 (br. s, 1 H, OH), 2.22–2.06 H, one proton in CH2 and 3 CH2), 0.78 (t, J = 6.5 Hz, 3 H, CH3)
(m, 1 H, CH2), 2.05–1.88 (m, 1 H, CH2), 0.80 (t, J = 7.4 Hz, 3 H,
ppm. 13C NMR (75 MHz, CDCl3): δ = 143.0, 140.9, 128.1, 127.4,
125.6, 117.1, 79.7, 39.3, 31.6, 29.5, 23.6, 22.5, 14.0 ppm. IR (neat):
CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 142.7, 140.6, 128.1,
127.4, 125.7, 117.3, 79.9, 32.1, 8.1 ppm. IR (neat): ν = 3557, 3465, ν = 3560, 3470, 3087, 3060, 3028, 2955, 2928, 2856, 1621, 1494,
˜
˜
3087, 3060, 3028, 2974, 2938, 2880, 1621, 1493, 1447, 1376, 1348,
1447, 1377, 1328, 1261, 1127, 1094, 1062, 1032 cm–1. MS (70 eV,
1311, 1271, 1199, 1126, 1077, 1055, 1032 cm–1. MS (70 eV, EI): m/z
EI): m/z (%) = 298 (3.30) [M(81Br)]+, 296 (3.29) [M(79Br)]+, 211
2282
www.eurjoc.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 2278–2285

2-Bromoalken-3-ols by Bromohydroxylation
(100). HRMS: calcd. for C15H2179BrO [M]+ 296.0776; found
296.0774.
1032, 1001 cm–1. MS (70 eV, EI): m/z (%)
= 290 (21.41)
[M(81Br)]+, 288 (21.92) [M(79Br)]+, 209 (100).
1
(E)-3j: Liquid. H NMR (300 MHz, CDCl3): δ = 7.39–7.26 (m, 3
5-(1-Bromovinyl)nonen-5-ol (2m) and 2-Bromo-3-n-butyl-2-hepten-1-
ol (3m): The reaction of 3-butylhepta-1,2-diene (1m; 90.9 mg,
0.6 mmol) and NBS (106.9 mg, 0.6 mmol) in 1,4-dioxane (2.0 mL)
and H2O (2.0 mL) at room temp. for 25 h afforded 2m (60.0 mg,
40%) and 3m (33.2 mg, 22%) (petroleum ether/ethyl acetate, 30:1).
H, ArH), 7.18–7.11 (m, 2 H, ArH), 4.13 (d, J = 6.3 Hz, 2 H,
CH2O), 2.59 (t, J = 7.4 Hz, 2 H, =CCH2), 2.10–1.96 (m, 1 H, OH),
1.40–1.19 (m, 8 H, 4 CH2), 0.85 (t, J = 6.8 Hz, 3 H, CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 144.4, 139.6, 128.4, 128.0, 127.6,
124.7, 65.6, 39.0, 31.5, 28.9, 26.7, 22.5, 14.0 ppm. IR (neat): ν =
˜
2m: Liquid. 1H NMR (300 MHz, CDCl3): δ = 5.90 (d, J = 1.8 Hz,
1 H, =CH), 5.58 (d, J = 2.1 Hz, 1 H, =CH), 1.86–1.71 (m, 3 H,
OH and CH2), 1.65–1.48 (m, 2 H, CH2), 1.40–1.18 (m, 8 H, 4 CH2),
0.90 (t, J = 6.9 Hz, 6 H, 2 CH3) ppm. 13C NMR (75 MHz, CDCl3):
3373, 2955, 2926, 2857, 1628, 1597, 1492, 1462, 1442, 1378, 1230,
1206, 1073, 1009 cm–1. MS (70 eV, EI): m/z (%) = 298 (8.67)
[M(81Br)]+, 296 (8.86) [M(79Br)]+, 129 (100). HRMS: calcd. for
C15H2179BrO [M]+ 296.0776; found 296.0775.
δ = 138.9, 116.9, 78.9, 38.7, 25.2, 22.9, 14.0 ppm. IR (neat): ν =
˜
2-Bromo-3-phenyl-1,5-hexadien-3-ol (2k) and (E)-2-Bromo-3-phenyl-
2,5-hexadien-1-ol [(E)-3k]: The reaction of hexa-1,2,5-trien-3-ylben-
zene (1k; 15.1 mg, 2.0 mmol) and NBS (357.5 mg, 2.0 mmol) in 1,4-
dioxane (6.8 mL) and H2O (6.8 mL) at room temp. for 12 h af-
forded 2k (306.5 mg, 60%) and (E)-3k (36.4 mg, 7%) (petroleum
ether/ethyl acetate, 20:1 Ǟ 10:1). The ratio of 2k/(E)-3k was 88:12
3482, 2957, 2931, 2872, 1622, 1467, 1379, 1344, 1290, 1248, 1149,
1089, 1041 cm–1. MS (70 eV, EI): m/z (%) = 250 (0.31) [M(81Br)]+,
248 (0.28) [M(79Br)]+, 191 (100). C11H21BrO (246.06): calcd. C
53.02, H 8.49; found C 53.11, H 8.52.
3m: Liquid. 1H NMR (300 MHz, CDCl3): δ = 4.33 (d, J = 6.6 Hz,
2 H, CH2O), 2.30–2.12 (m, 4 H, 2 CH2), 1.95 (t, J = 6.3 Hz, 1 H,
OH), 1.50–1.20 (m, 8 H, 4 CH2), 1.00–0.81 (m, 6 H, 2 CH3) ppm.
13C NMR (75 MHz, CDCl3): δ = 143.1, 122.2, 64.4, 36.6, 32.4,
1
as determined by H NMR spectroscopy using CH2Br2 as the in-
ternal standard.
1
2k: Liquid. H NMR (300 MHz, CDCl3): δ = 7.54–7.44 (m, 2 H,
31.3, 29.5, 22.8, 22.6, 14.0, 13.9 ppm. IR (neat): ν = 3355, 2957,
˜
2930, 2861, 1638, 1466, 1379, 1233, 1067, 1004 cm–1. MS (70 eV,
EI): m/z (%) = 250 (9.93) [M(81Br)]+, 248 (10.19) [M(79Br)]+, 109
(100). HRMS: calcd. for C11H2181BrO [M]+ 250.0755; found
250.0758.
ArH), 7.42–7.22 (m, 3 H, ArH), 6.07 (d, J = 2.4 Hz, 1 H, one
proton in =CH2), 5.83–5.64 (m, 2 H, one proton in =CH2 and
=CH), 5.21 (d, J = 4.2 Hz, 1 H, one proton in =CH2), 5.16 (s, 1
H, one proton in =CH2), 3.08 (dd, J = 14.1 and 6.6 Hz, 1 H, one
proton in CH2), 2.79 (dd, J = 13.8 and 7.5 Hz, 1 H, one proton in
CH2), 2.63 (s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ =
142.4, 139.4, 132.6, 128.2, 127.7, 125.8, 120.2, 117.7, 78.5,
2-Bromo-1,1-diphenyl-2-buten-1-ol (2n) and 3-Bromo-4,4-diphenyl-3-
buten-2-ol (3n): The reaction of 1,1-diphenylbuta-1,2-diene (1n;
123.3 mg, 0.6 mmol) and NBS (106.7 mg, 0.6 mmol) in 1,4-dioxane
(2.0 mL) and H2O (2.0 mL) at room temp. for 26 h afforded 2n
(37.2 mg, 21%) and 3n (81.5 mg, 45%) (petroleum ether/ethyl acet-
ate, 40:1 Ǟ 10:1).
43.7 ppm. IR (neat): ν = 3545, 3076, 3028, 2979, 1640, 1620, 1494,
˜
1447, 1345, 1176, 1128, 1091, 1061 cm–1. MS (70 eV, EI): m/z (%) =
254 (0.22) [M(81Br)]+, 252 (0.22) [M(79Br)]+, 211 (100). C12H13BrO
(252.01): calcd. C 56.94, H 5.18; found C 56.80, H 5.28.
1
1
2n: Liquid. H NMR (300 MHz, CDCl3): δ = 7.40–7.20 (m, 10 H,
(E)-3k: Liquid. H NMR (300 MHz, CDCl3): δ = 7.45–7.27 (m, 3
ArH), 6.30 [q, J = 7.7, 0.4 H, =CH(E)], 5.43 [q, J = 6.6 Hz, 0.6 H,
=CH(Z)], 3.26 [s, 0.4 H, OH(E)], 3.20 [s, 0.6 H, OH(Z)], 1.72 [d, J
= 6.9 Hz, 1.8 H, CH3(Z)], 0.82 [d, J = 7.8 Hz, 1.2 H, CH3(E)] ppm.
H, ArH), 7.20–7.13 (m, 2 H, ArH), 5.80–5.64 (m, 1 H, =CH), 5.12–
5.49 (m, 2 H, =CH2), 4.18 (d, J = 5.7 Hz, 2 H, CH2O), 3.36 (dt, J
= 6.6 and 1.5 Hz, 2 H, CH2), 1.99 (t, J = 6.5 Hz, 1 H, OH) ppm.
13C NMR (75 MHz, CDCl3): δ = 141.6, 139.3, 132.8, 128.4, 128.1,
IR (neat): ν = 3543, 3059, 3026, 3026, 2920, 2855, 1653, 1598, 1490,
˜
1447, 1329, 1281, 1162, 1113, 1063, 1033, 1010 cm–1. MS (70 eV,
EI): m/z (%) = 304 (3.46) [M(81Br)]+, 302 (3.53) [M(79Br)]+, 183
(100). HRMS: calcd. for C16H1579BrO [M]+ 302.0306; found
302.0310.
127.7, 126.0, 117.0, 65.6, 43.4 ppm. IR (neat): ν = 3385, 3079, 3059,
˜
2921, 2872, 1638, 1600, 1491, 1442, 1432, 1412, 1227, 1072,
1000 cm–1. MS (70 eV, EI): m/z (%) = 254 (5.44) [M(81Br)]+, 252
(5.33) [M(79Br)]+, 155 (100). HRMS: calcd. for C12H1379BrO [M]+
252.0150; found 252.0148.
1
3n: Liquid. H NMR (300 MHz, CDCl3): δ = 7.31–7.01 (m, 10 H,
ArH), 4.47 (q, J = 6.2 Hz, 1 H, CHO), 2.07 (br. s, 1 H, OH), 1.31
(d, J = 6.3 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
142.5, 142.1, 140.2, 132.3, 128.9, 128.6, 128.5, 128.0, 127.7, 127.4,
2-Bromo-1,1-diphenyl-2-propen-1-ol (2l) and 2-Bromo-3,3-diphenyl-
2-propen-1-ol (3l): The reaction of 1,1-diphenylpropa-1,2-diene (1l;
192.4 mg, 1.0 mmol) and NBS (178.3 mg, 1.0 mmol) in 1,4-dioxane
(3.4 mL) and H2O (3.4 mL) at room temp. for 13 h afforded 2l
(105.9 mg, 37%) and 3l (56.6 mg, 20%) (petroleum ether/ethyl acet-
ate, 400:1 Ǟ 100:1 Ǟ 20:1).
67.9, 23.2 ppm. IR (neat): ν = 3396, 3055, 3025, 2978, 2928, 1597,
˜
1576, 1491, 1443, 1371, 1285, 1174, 1133, 1074, 1030 cm–1. MS
(70 eV, EI): m/z (%)
=
304 (5.06) [M(81Br)]+, 302 (5.22)
[M(79Br)]+, 223 (100). HRMS: calcd. for C16H15 79BrO [M]+
302.0306; found 302.0305.
1
2l: Liquid. H NMR (300 MHz, CDCl3): δ = 7.45–7.26 (m, 10 H,
ArH), 5.81 (d, J = 2.1 Hz, 1 H, =CH), 5.33 (d, J = 2.4 Hz, 1 H,
=CH), 3.18 (s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ =
General Procedure for the Elimination of HBr from 2 To Afford
Propargylic Alcohol 4[9]
142.5, 140.6, 128.1, 127.9, 127.6, 122.1, 83.1 ppm. IR (neat): ν =
˜
3546, 3060, 3027, 1620, 1598, 1492, 1447, 1368, 1336, 1163, 1126,
1038, 1002 cm–1. MS (70 eV, EI): m/z (%) = 290 (5.35) [M(81Br)]+,
288 (5.33) [M(79Br)]+, 183 (100). C15H13BrO (288.01): calcd. C
62.30, H 4.53; found C 62.31, H 4.43.
1-Phenyl-3-butyn-2-ol (4a): TBAF (1.2 mL, 1 m in THF, 1.2 mmol)
was slowly added to a solution of 2a (91.0 mg, 0.4 mmol) and
DMF (4 mL). After continuous stirring at room temp. for 12 h, the
reaction was complete, as monitored by TLC. Then the mixture
was diluted with diethyl ether (20 mL), quenched by the addition
of saturated aqueous NH4Cl (5 mL), washed with water, and dried
1
3l:[15] Liquid. H NMR (300 MHz, CDCl3): δ = 7.48–7.05 (m, 10
H, ArH), 4.40 (s, 2 H, CH2O), 2.36 (s, 1 H, OH) ppm. 13C NMR
(75 MHz, CDCl3): δ = 144.7, 142.1, 139.7, 129.0, 128.4, 128.1, with anhydrous Na2SO4. Concentration and column chromatog-
127.9, 127.7, 125.6, 65.9 ppm. IR (neat): ν = 3386, 3056, 3026, raphy on silica gel (petroleum ether/ethyl acetate, 10:l) afforded
˜
1
2926, 2870, 1597, 1576, 1493, 1443, 1381, 1290, 1209, 1173, 1086,
4a[16] (33.9 mg, 58%) as a liquid. H NMR (300 MHz, CDCl3): δ
Eur. J. Org. Chem. 2011, 2278–2285
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2283

W. Kong, B. Guo, C. Fu, S. Ma
FULL PAPER
= 7.40–7.20 (m, 5 H, ArH), 4.56 (td, J = 6.5 and 2.1 Hz, 1 H,
acetate, 30:1) on silica gel afforded 6a (47.2 mg, 70%) as a liquid.
CHO), 3.08–2.93 (m, 2 H, ArCH2), 2.47 (d, J = 2.4 Hz, 1 H, 1H NMR (300 MHz, CDCl3): δ = 7.48–7.15 (m, 10 H, ArH), 5.37
CϵCH), 2.19 (br. s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3):
δ = 136.2, 129.7, 128.4, 126.9, 84.1, 73.8, 62.9, 43.7 ppm. IR (neat):
(d, J = 1.2 Hz, 1 H, =CH), 5.34 (s, 1 H, =CH), 4.90–4.80 (m, 1 H,
CHO), 2.95 (dd, J = 14.0 and 3.8 Hz, 1 H, one proton in ArCH2),
2.68 (dd, J = 14.0 and 8.6 Hz, 1 H, one proton in ArCH2), 1.93
(br. s, 1 H, OH) ppm. 13C NMR (75 MHz, CDCl3): δ = 150.9,
139.8, 138.1, 129.4, 128.43, 128.40, 127.7, 126.8, 126.5, 113.0, 74.3,
ν = 3539, 3374, 3288, 3086, 3063, 3030, 2950, 2926, 2860, 2117,
˜
1602, 1496, 1454, 1435, 1390, 1335, 1289, 1079, 1032, 1004 cm–1.
MS (70 eV, EI): m/z (%) = 146 (1.65) [M]+, 128 (16.15) [M –
H2O]+, 91(100).
42.7 ppm. IR (neat): ν = 3423, 3063, 3028, 2907, 2859, 1630, 1597,
˜
1576, 1495, 1454, 1263, 1028 cm–1. MS (70 eV, EI): m/z (%) = 224
(29.25) [M]+, 105 (100). HRMS: calcd. for C16H16O [M]+ 224.1201;
found 224.1192.
1,1-Diphenyl-2-butyn-1-ol (4n) and (Z)-2-Bromo-1,1-diphenyl-2-
buten-1-ol [(Z)-2n]: The reaction of 2n (391.7 mg, 1.29 mmol) and
TBAF (3.9 mL, 1 m in THF, 3.9 mmol) in DMF (13.0 mL) at room
temp. for 24 h afforded (Z)-2n (198.8 mg, 51%) and 4n (17.0 mg,
6%) (petroleum ether/ethyl acetate, 100:l Ǟ 50:1 Ǟ 30:1).
3-Styryl-1-phenyl-3-buten-2-ol (7a): The reaction of K3PO4
(222.6 mg, 1.05 mmol), Pd(OAc)2 (2.1 mg, 0.009 mmol), styryl-
boronic acid (89.0 mg, 0.6 mmol), 2a (68.3 mg, 0.3 mmol), 1,4-di-
oxane (2 mL), PPh3 (4.7 mg, 0.018 mmol), and H2O (16.5 μL,
0.9 mmol) at 110 °C for 6 h afforded 7a (42.0 mg, 56%) (petroleum
ether/ethyl acetate, 20:1) as a liquid. 1H NMR (300 MHz, CDCl3):
δ = 7.48–7.38 (m, 2 H, ArH), 7.37–7.18 (m, 8 H, ArH), 6.82 (d, J
= 16.5 Hz, 1 H, =CH), 6.75 (d, J = 16.5 Hz, 1 H, =CH), 5.29 (s, 2
H, =CH2), 4.72 (d, J = 7.5 Hz, 1 H, CHO), 3.09 (dd, J = 14.0 and
3.8 Hz, 1 H, one proton in ArCH2), 2.84 (dd, J = 13.7 and 8.6 Hz,
1 H, one proton in ArCH2), 1.87 (s, 1 H, OH) ppm. 13C NMR
(75 MHz, CDCl3): δ = 147.8, 138.3, 137.1, 129.4, 128.9, 128.6,
128.5, 128.0, 127.7, 126.6, 126.4, 114.9, 72.7, 43.2 ppm. IR (neat):
4n:[17] Liquid. 1H NMR (300 MHz, CDCl3): δ = 7.70–7.50 (m, 4
H, ArH), 7.40–7.20 (m, 6 H, ArH), 2.52 (br. s, 1 H, OH), 1.97 (s,
3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 145.4, 128.1,
127.5, 126.0, 83.7, 82.1, 74.4, 3.9 ppm. IR (neat): ν = 3404, 3084,
˜
3060, 3027, 2972, 2920, 2852, 2233, 1599, 1490, 1449, 1382, 1350,
1280, 1180, 1157, 1142, 1105, 1077, 1032, 1011 cm–1. MS (70 eV,
EI): m/z (%) = 222 (40.04) [M]+, 207 (100) [M – CH3]+.
(Z)-2n: Solid; m.p. 79.5–80.6 °C. 1H NMR (300 MHz, CDCl3): δ =
7.35–7.18 (m, 10 H, ArH), 5.44 (q, J = 6.5 Hz, 1 H, =CH), 3.20 (s,
1 H, OH), 1.72 (d, J = 6.3 Hz, 3 H, CH3) ppm. 13C NMR (75 MHz,
CDCl3): δ = 143.5, 136.4, 129.1, 128.0, 127.8, 127.7, 83.3, 17.3 ppm.
ν = 3562, 3425, 3027, 2922, 2852, 1602, 1494, 1451, 1078 cm–1. MS
˜
(70 eV, EI): m/z (%) = 250 (1.77) [M]+, 91 (100). HRMS: calcd. for
IR (KBr): ν = 3547, 3059, 3028, 2918, 2854, 1651, 1598, 1491, 1447,
˜
1374, 1331, 1281, 1201, 1160, 1117, 1063, 1033, 1010 cm–1. MS
C18H18O [M]+ 250.1358; found 250.1357.
(70 eV, EI): m/z (%)
=
304 (3.69) [M(81Br)]+, 302 (3.80)
[M(79Br)]+, 183 (100). C16H15BrO (302.03): calcd. C 63.38, H 4.99;
found C 63.58, H 5.05.
Supporting Information (see footnote on the first page of this arti-
1
cle): H and 13C NMR spectra of all compounds.
Procedure for the Sonogashira Coupling of 2a. Synthesis of 3-Meth-
ylene-1,5-diphenyl-4-butyn-2-ol (5a): [PdCl2(PPh3)2] (11.0 mg,
0.015 mmol), CuI (3.1 mg, 0.015 mmol), 2a (68.1 mg, 0.30 mmol),
benzene (2 mL), ethynylbenzene (62.5 mg, 0.6 mmol), and nBuNH2
(110.2 mg, 1.5 mmol) were sequentially added to a Schlenk tube at
room temperature. After stirring for 14 h, the reaction was com-
plete, as monitored by TLC. The residue was purified by silica gel
column chromatography (petroleum ether/ethyl acetate, 10:1) to
Acknowledgments
Financial support from the National Natural Science Foundation
of China (No. 20732005 and 20972135) and the Zhejiang Provincial
Science Foundation of China (No. Y4090217) is greatly appreci-
ated. S. M. is a Qiu Shi Adjunct Professor at Zhejiang University.
We thank Mr. Yu Liu in this group for reproducing the results
presented in Entries 2, 7, and 11 in Table 2 and 1m in Scheme 1.
1
give 5a (68.1 mg, 92%) as a liquid. H NMR (300 MHz, CDCl3):
δ = 7.53–7.42 (m, 2 H, ArH), 7.41–7.18 (m, 8 H, ArH), 5.53 (s, 1
H, =CH), 5.48 (s, 1 H, =CH), 4.49–4.36 (m, 1 H, CHO), 3.16 (dd,
J = 13.5 and 5.1 Hz, 1 H, one proton in ArCH2), 2.95 (dd, J =
13.7 and 7.7 Hz, 1 H, one proton in ArCH2), 2.00 (br. s, 1 H, OH)
ppm. 13C NMR (75 MHz, CDCl3): δ = 137.5, 133.6, 131.6, 129.5,
128.44, 128.39, 128.3, 126.6, 122.8, 121.4, 91.8, 86.7, 75.2,
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42.6 ppm. IR (neat): ν = 3563, 3426, 3083, 3061, 3028, 2922, 1605,
˜
1490, 1454, 1442, 1384, 1313, 1180, 1079, 1030 cm–1. MS (70 eV,
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C18H16O [M]+ 248.1201; found 248.1201.
Procedure for the Suzuki Coupling Reaction
1,3-Diphenyl-3-buten-2-ol (6a): K3PO4 (222.6 mg, 1.05 mmol) was
added to a rubber-capped Schlenk vessel. This vessel was flame-
dried under vacuum and backfilled with nitrogen three times. Then
Pd(OAc)2 (2.0 mg, 0.009 mmol), phenylboronic acid (73.0 mg,
0.6 mmol), dioxane (1 mL), 2a (68.6 mg, 0.3 mmol), dioxane
(1 mL), PPh3 (4.8 mg, 0.018 mmol), and water (16.5 μL, 0.9 mmol)
were added sequentially to the Schlenk vessel at room temperature.
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bath. After 48 h, the reaction was complete, as monitored by TLC.
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2284
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 2278–2285

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Received: December 14, 2010
Published Online: March 7, 2011
Eur. J. Org. Chem. 2011, 2278–2285
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2285