One-pot, solvent-free regioselective addition reactions of propargyl bromide to carbonyl compounds mediated by Zn-Cu couple

Article abstract of DOI:10.1016/j.tet.2009.08.051

A Barbier-type propargylation of carbonyl compounds with propargyl bromide has been achieved with reactive zinc-copper couple under solvent-free conditions. The reaction of aldehydes with propargyl bromide produced the unique homopropargyl alcohols in excellent yields at room temperature without the formation of homoallenyl alcohols. The ketones reacted with propargyl bromide to give the corresponding homopropargyl alcohols in good to excellent yields at -14 to -16 °C. The advantages of this method are excellent yields, short reaction time, high regioselectivity, and avoidance of the use of organic solvents.

Full text of DOI:10.1016/j.tet.2009.08.051

Tetrahedron 65 (2009) 8683–8689
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
One-pot, solvent-free regioselective addition reactions of propargyl
bromide to carbonyl compounds mediated by Zn–Cu couple
,
b
,
a
a
a
Xiaofang Ma a, Jin-Xian Wang a , Shunxi Li , Ke-Hu Wang , Danfeng Huang
*
a Institute of Chemistry, Department of Chemistry, Northwest Normal University, 967 Anning Road (E.), Lanzhou 730070, PR China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730070, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 May 2009
Received in revised form 19 August 2009
Accepted 21 August 2009
Available online 26 August 2009
A Barbier-type propargylation of carbonyl compounds with propargyl bromide has been achieved with
reactive zinc–copper couple under solvent-free conditions. The reaction of aldehydes with propargyl
bromide produced the unique homopropargyl alcohols in excellent yields at room temperature without the
formation of homoallenyl alcohols. The ketones reacted with propargyl bromide to give the corresponding
homopropargyl alcohols in good to excellent yields at ꢀ14 to ꢀ16 ꢁC. The advantages of this method are
excellent yields, short reaction time, high regioselectivity, and avoidance of the use of organic solvents.
Ó 2009 Published by Elsevier Ltd.
1. Introduction
Moreover, in the solid state, molecules of the reaction are arranged
in order, the directional reaction could be carried out and the
In recent years, homopropargyl alcohols have received much
attention as synthetic intermediates in organic synthesis and as the
structural moieties in many biologically active compounds.1
Numerous methods of propargylation of carbonyl compounds with
propargyl bromide, such as using effective catalysts, aqueous phase
reactions,2 microwave,2a,b and ultrasound irradiation,3 have been
reported. The Barbier-type reactions have been widely applied to
the synthesis of homopropargyl in laboratories and industries.
Many metals including Sb,4 Cr,5 In,2c,6 Mg,1a Mn,7 Sn,8 Pb,9 Ti,10 and
Zn11 have been reported to be effective in mediating the coupling
between propargyl halides and carbonyl compounds to give the
corresponding homopropargyl alcohols. In 2005, a new, efficient,
and regioselective addition reaction of propargyl bromide to car-
bonyl compounds with gallium catalyzed by indium in THF was
reported.12a However, these methods require long reaction time
and use of organic solvents, such as THF, DMSO, and DMF, to
improve the yields. The use of a great deal of organic solvents can
potentially lead to some environmental pollution. Although the
regiocontrolled synthesis of homopropargyl alcohols has been
extensively studied, there are still not many satisfactory methods
for the selective propargylation.8b,12a–c
reaction selectivity could be improved. In addition, in the solid-state
chemical reaction, on account of the topology of control theory, the
reaction would be performed in the absence of solvents, the higher
concentration of reactants in the absence of solvents usually leads to
more favorable kinetics than in solution. So it is possible for prop-
argylation2b,3,12 of carbonyl compounds selectively to introduce
carbon–carbon triple bond into organic molecules under solvent-
free conditions.
The reactivity of Zn–Cu couple in organic reactions has been
described.14,15 Zn–Cu couple has been considered as a moderate,
non-toxic, low-cost metal mediator in organic reaction, and has the
following advantages: simple post-processing, complete recovery of
copper, and environmentally benign. With the great interest and
demands of green chemistry,16 herein we report an efficient Barbier-
type reaction of carbonyl compounds with propargyl bromide
mediated by Zn–Cu couple under solvent-free conditions to syn-
thesize the homopropargyl alcohols (Scheme 1).
OH
r.t
R1
R2 = H
In the solid organic reactions,13 the micro-environment of
reaction system is different from the environment of the reaction
solution as no solvent molecules are involved. This often results in
increase of reaction mixture concentration and improved efficiency.
O
Zn-Cu couple
Br
R1 R2
+
OH
R2
solvent-free
OH
R2
-14 to -16 ºC
R2 = Me, Et
•
+
R1
R1
R1 = Ph, Aryl, Heterocyclic, Aliphatic; R2 = H, Me, Et.
* Corresponding author.
Scheme 1. Zn–Cu couple mediated regioselective propargylation of carbonyl com-
E-mail address: wangjx@nwnu.edu.cn (J.-X. Wang).
pounds with propargyl bromide under solvent-free conditions.
0040-4020/$ – see front matter Ó 2009 Published by Elsevier Ltd.
doi:10.1016/j.tet.2009.08.051

8684
X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
Table 2
2. Results and discussion
Zn–Cu couple mediated regioselective propargylation of various aldehydes with
propargyl bromidea
We found that propargylation of aldehydes mediated by Zn–Cu
couple generated homopropargyl alcohols under solvent-free
conditions at room temperature in excellent yields.
O
OH
Zn-Cu couple
+
Br
R
H
R
solvent-free, r.t.
First, to investigate the reactivity and regioselectivity of Zn–Cu
couples, a variety of metals and solvents were examined in the
reactions of benzaldehyde with propargyl bromide and the results
are summarized in Table 1.
1a-t
2
3a-t
Entry
1
RCHO
CHO
Productb
Time (min)
30
Yieldc (%)
3a
85 (7816b
88 (8516b
86 (7916b
84 (8116b
83 (8216b
)
Table 1
Effects of the mediator and the amount of solvents on the formation of 3aa
CHO
2
3
4
5
3b
3c
3d
3e
30
30
30
45
)
)
)
)
OH
O
H3CO
H3CO
Cl
Zn-Cu couple
+
Br
CHO
H
solvent-free, r.t.
OCH3
1a
2
3a
CHO
Entry
Mediator
Solvent
Time (h)
Yieldb (%)
CHO
1
2
3
4
5
6
7
8
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Mc–Cu
Sn–Cu
Mg–Cu
Me
H2O
H2O
Et2O
CH2Cl2
CH3CN
EtOH
DMSO
THF
8
Trace
20
25
40
42
54
60
75
70
16
16
16
3
6
1.2
3
1.2
0.5
16
1.2
1.5
5–17
1
Cl
Cl
CHO
6
3f
45
83
Cl
CHO
7
8
3g
3h
45
45
90 (8416b
)
9
DMF
Cl
10
11
12
13
14
15
16
None
None
None
None
None
None
None
85
NRd
56
Cl
CHO
89
12
NRd
60
CHO
Sn
Zn
9
3i
3j
3k
3l
45
25
25
25
89 (8716b
88 (8016b
84 (7816b
83
)
)
)
0.42
78
Cl
Br
a
Reaction conditions: 1a (2.0 mmol),
2 (3.0 mmol), Zn–Cu couple or metal
CHO
CHO
(4 mmol), solvent (2 mL), at room temperature.
10
11
12
b
Isolated yields of homopropargyl alcohol 3a after chromatography.
c
M¼Al–Cu, Fe–Cu, Mn–Cu, and Cd–Cu.
d
NR: no reaction. Almost all of the benzaldehyde was recycled.
e
M¼Cd, Ni, Mn, Co, Fe, Al, W, Pb, Ti.
Br
CHO
As shown in Table 1, propargylation of benzaldehyde mediated
by Zn–Cu couple in H2O, Et2O, CH2Cl2 or CH3CN did not give the
desired addition product even after prolonged reaction time (Table
1, entries 1–5). The product was produced in EtOH and DMSO in
moderate yields (Table 1, entries 6 and 7). The same reaction gave
the corresponding homopropargyl alcohol in THF and DMF in good
yields (75% and 70%, respectively) (Table 1, entries 8 and 9). The
yield of homopropargyl alcohol was enhanced to 85% using Zn–Cu
couple as the mediator under the solvent-free condition (Table 1,
entry 10). Different M–Cu couples or metals were tested to mediate
the propargylation of benzaldehyde in the absence of solvent.
Al–Cu, Fe–Cu, Mn–Cu, and Cd–Cu couples were not effective to
produce the desired products (Table 1, entry 11). Using Sn–Cu and
Mg–Cu couples as mediators in the absence of solvent, the homo-
propargyl alcohols were gained in 56% and 12% yields, respectively
(Table 1, entries 12 and 13). It was found that various metals, such
as Cd, Ni, Mn, Co, Fe, Al, W, Pb, and Ti, were not effective to mediate
the propargylation of benzaldehyde (Table 1, entry 14). When the
mediator was Sn, the product was produced in moderate yield
(Table 1, entry 15). The product in 78% yield was obtained when Zn
powder was used as mediator under solvent-free condition (Table
1, entry 16). So the optimized conditions are Zn–Cu couple as me-
diator under solvent-free condition at room temperature.
Br
13
3m
30
80 (6816b
)
CHO
14
15
16
17
18
3n
3o
3p
3q
3r
30
30
55
60
55
90 (7916b
90 (8016b
85 (7516b
84 (7816b
88 (8016b
)
)
)
)
)
CHO
O
S
CHO
CHO
CHO
CHO
Br
CHO
19
3s
3t
55
55
80
H3CO
20
CHO
60 (7416b
)
a
All reactions were conducted on the scale of 2 mmol of aldehydes with 3 mmol
of propargyl bromide, and 4 mmol of Zn–Cu couple at room temperature.
The scope of this reactionwas studied with various aldehydes and
the experiment results are listed in Table 2. Aromatic aldehydes,
whether 2-substituted, 3-substituted or 4-substituted benzalde-
hyde, reacted, respectively, with propargyl bromide to give the
All products were characterized by IR, 1H NMR, 13C NMR, MS, and elemental
b
analyses for all new compounds.
c
Isolated yields.

X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
8685
Table 4
corresponding homopropargyl alcohols in good yields (Table 2,
entries 2–4, 7–12). 2,4-Dichlorobenzaldehyde or 2,6-dichloro-
benzaldehyde reacted with propargyl bromide to produce the
product in good yields (Table 2, entries 5 and 6). Moreover, anthra-
cene-10-carbaldehyde reacted with propargyl bromide to produce
the product in 80% yield (Table 2, entry 13). These results clearly
show that the substituent on the phenyl ring, whether electron-
donating or electron-withdrawing, has no dramatic influence on the
product yields. Moreover, the position of the substituent on the
phenyl ring also has no dramatic influence on the product yields.
Heterocyclic aldehydes reacted with propargyl bromide to afford the
corresponding homopropargyl alcohols in good yields (90% and 90%,
Zn–Cu couple mediated regioselective propargylation of various ketones with
propargyl bromidea
O
OH
OH
Zn-Cu couple
+
Br
R1
R2
•
R1
+
R1
R2
solvent-free, -14 to -16 ºC
R2
4a-p
2
5a-p
6a-p
Entry
1
R1COR2
Productb
Time (min)
30
Yieldc [% (5a–p/6a–p)]
O
5a
92 (100:0), 75d
O
respectively) (Table 2, entries 14 and 15). a,b-Unsaturated aldehydes
2
3
5b
5c
35
35
92 (100:0), 74d
92 (100:0), 74d
were also propargylated in good yields (Table 2, entries 16–19), only
the 1,2-addition products were obtained regioselectively. When the
substrate was aliphatic aldehydes, homopropargyl alcohol was also
obtained in 60% yield (Table 2, entry 20).
O
Br
Cl
Encouraged by the previous results, we further investigated the
propargylation of ketones mediated by Zn–Cu couple in the absence
of solvent at room temperature. First, we chose acetophenone as
substrate, a mixture of acetophenone, propargyl bromide, solvents,
Zn–Cu couple or metals was stirred. The results are summarized in
Table 3.
O
4
5
5d
5e
35
35
91 (100:0), 8116f
90 (100:0), 80d
O
Table 3
Effects of the mediator and the amount of solvents on the formation of 5a and 6aa
O
6
7
5fþ6f
40
30
91 (91:9), 75d
82 (100:0)
OH
OH
O
•
+
Zn-Cu or Metals
CH3
Br
+
CH3
CH3
O
solvent
r.t. or-14 to -16 ºC
5g
6a
5a
4a
2
O
Entry
Mediator
Solvent
Time (h)
Yieldb (%)
rt
ꢀ14 to ꢀ16 ꢁC
8
9
5h
5i
30
30
90 (100:0)
90 (100:0)
1
2
3
4
5
6
7
8
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn–Cu
Zn
H2O
Et2O
CH2Cl2
CH3CN
DMSO
THF
13
18
13
2
1.5
1.5
1
0.5
1
0.5
NRc
NRc
NRc
NRc
NRc
NRc
NRc
NRc
76 (84:16)
60 (91:9)
64 (82:18)
87 (85:15)
75 (100:0)
NRc
42 (100:0)
NRc
73 (100:0)
92 (100:0)
24 (100:0)
NRc
O
DMF
O
None
None
None
10
11
12
5j
30
30
33
90 (100:0)
90 (100:0)
80 (100:0)
9
10
O
Cu
a
O
Reaction conditions: 4a (2.0 mmol),
2 (3.0 mmol), Zn–Cu couple or metal
5k
5l
(4 mmol), and solvent (2 mL).
b
Isolated yields of homopropargyl alcohol 5a and homoallenyl alcohol 6a after
S
chromatography. Ratios were obtained in GC.
O
c
NR: no reaction. Almost all of the acetophenone was recycled.
S
It can be seen that the propargylation of acetophenone mediated
by Zn–Cu couple in H2O, Et2O, CH2Cl2 or CH3CN did not give the
addition product even after prolonged reaction time (Table 3, entries
1–4). When the solvent was DMSO, THF or DMF, the product was
a mixture of homopropargyl alcohol and homoallenyl alcohols in 76%
(5a/6a¼84:16), 60% (5a/6a¼91:9) and 64% (5a:6a¼82:18) yields,
respectively, at room temperature. But the homopropargyl alcohol
was regioselectively afforded when the temperature was decreased
to ꢀ14 to ꢀ16 ꢁC (Table 3, entries 5–7) except in THF. The reaction
proceeded smoothly in the absence of solvent at room temperature
for 0.5 h with good yield of 87% (5a/6a¼85:15). When the reaction
was performed at ꢀ14 to ꢀ16 ꢁC, the yield of the homopropargyl
alcohol was enhanced to 92% (5a/6a¼100:0) (Table 3, entry 8). When
using Cu, the reaction did not produce the addition product whether
at room temperature or at ꢀ14 to ꢀ16 ꢁC even after prolonged
reaction time (Table 3, entry 10). With Zn powder, the product was
generated in good yield (75%) at room temperature and 24% at ꢀ14 to
ꢀ16 ꢁC (Table 3, entry 9). According to our investigation, the efficient
13
14
5m
5n
30
30
85 (100:0)
O
O
87 (100:0), 7216f
O
O
15
5o
5p
45
38
85 (100:0), 70d
80 (100:0), 73d
16
a
All reactions were conducted on the scale of 2 mmol of ketones with 3 mmol of
propargyl bromide and 4 mmol of Zn–Cu couple at ꢀ14 to ꢀ16 ꢁC.
b
All products were identified by IR, 1H NMR, 13C NMR, MS, and elemental anal-
yses for all new compounds.
c
Yields of isolated products. Ratios were obtained in GC.
The reaction was mediated by Zn powder at room temperature.
d

8686
X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
conditions for the propargylation of acetophenone were at ꢀ14 to
ꢀ16 ꢁC mediated by Zn–Cu couple under the solvent-free conditions.
These results encouraged us to explore the propargylation of
various ketones mediated by Zn–Cu couple under solvent-free con-
ditions at ꢀ14 to ꢀ16 ꢁC. The experiment results are listed in Table 4.
As shown in Table 4, it can be seen that the aromatic ketones
reacted with propargyl bromide and generated the corresponding
homopropargyl alcohols at ꢀ14 to ꢀ16 ꢁC in excellent yields (Table
4, entries 1–5). If the substrate was benzophenone, a mixture of 5f
and 6f was gained in 91% (5f/6f¼91:9) yield (Table 4, entry 6). When
the ketones were 1-(naphthalen-2-yl)ethanone, 1-(4-biphenyl)-
ethanone, and 1-(9H-fluoren-7-yl)ethanone, the corresponding
products were obtained in excellent yields (Table 4, entries 7–9).
The results clearly showed that a substituent on the phenyl ring has
no significant influence on the product yields, but has a little in-
fluence on the selectivity of the products. If the substrates were
heterocyclic ketones, the corresponding homopropargyl alcohols
added. The resulting mixture was stirred and the reaction was
monitored by TLC. After complete conversion, saturated NH4Cl
(15 mL) solution was poured into the mixture. The mixture was
extracted with Et2O (3ꢂ10 mL) and the organic layer was separated,
dried over anhydrous MgSO4, and evaporated. The pure product
was obtained by column chromatograph of the crude mixture on
silica gel using petroleum/ethyl acetate as an eluent. All the isolated
products were characterized by IR, 1H NMR, 13C NMR, and MS, and
elemental analysis for all the new compounds.
4.3. Typical experimental procedure for the synthesis
of Zn–Cu couple
Zinc powder (178 mmol) and distilled water (80 mL) were
placed into a 100 mL round-bottom flask equipped with a stir bar.
With stirring, add HCl (37%, 2ꢂ1 mL) over 10 min. Then anhydrous
CuSO4 (30 mmol) was added into the flask with stirring and went
on stirring for about 15 min. Finally, the mixture was filtered and
the solid was washed with water (3ꢂ30 mL), acetone (3ꢂ10 mL),
and ethyl ether (2ꢂ10 mL). Transfer the solid to a flask equipped
with vacuum take-off and dry under vacuum for 3 h at 100 ꢁC.
were obtained in high yields (Table 4, entries 10–12). For a,b-un-
saturated ketones, only the 1,2-addition products were obtained
regioselectively in 90% and 80% good yields, respectively (Table 4,
entries 11 and 16). Aliphatic ketones also produced the addition
products in good yields (Table 4, entries 13–16).
Compared to the propargylation of ketones mediated by Zn
powder at room temperature, when the propargylation of ketones
was performed at ꢀ14 to ꢀ16 ꢁC mediated by Zn–Cu couple in the
absence of solvent, homopropargyl alcohols were regioselectively
produced in good to excellent yields. The yields of the products
were improved 7–17% and the reaction time was shortened.
4.3.1. 1-Phenylbut-3-yn-1-ol 3a. Colorless oil,17 IR (
3295, 3032, 2912, 2119, 1956, 1684, 1604, 1451, 862, 756, 701, 642;
1H NMR (400 MHz, CDCl3):
¼7.41–7.26 (m, 5H), 4.88 (t, J¼6.4 Hz,
1H), 2.65 (q, J¼6.4, 2.8 Hz, 2H), 2.40 (s, 1H), 2.08 (t, J¼2.8 Hz, 1H);
n
/cmꢀ1): 3393,
d
13C NMR (100 MHz, CDCl3):
d
¼142.4, 128.5, 128.0, 125.7, 80.6, 72.3,
71.0, 29.4; EIMS (m/z, %) 146 (Mþ), 107, 79, 77, 51, 39.
3. Conclusion
4.3.2. 1-(4-Methoxyphenyl)but-3-yn-1-ol 3b. Colorless oil,18 IR
(n
/cmꢀ1): 3422, 3291, 2912, 2838, 2118, 1646, 1613, 1514,1248, 1034,
We report an efficient, one-pot, and green synthesis of homo-
propargyl alcohols mediated by Zn–Cu couple under solvent-free
conditions in good to excellent yields. In contrast to the methods in
the literature, the main advantages of this method are: the excel-
lent yields when Zn–Cu couple is used as mediator (the yields rise
as high as 80–90% from 68–87% for aldehydes and the yields rise as
high as 80–92% from 70–81% for ketones), short reaction time, high
regioselectivity, and avoidance of the use of organic solvent. Our
work showed that substantial progress could be made in organic
reactions under the solvent-free conditions. This method could be
potentially applied to the synthesis of natural products or other
biological intriguing compounds.
833, 644; 1H NMR (400 MHz, CDCl3):
d
¼7.33–7.26 (m, 2H), 6.90–
6.87 (m, 2H), 4.83 (q, J¼6.0, 2.8 Hz, 1H), 3.80 (s, 3H), 2.64–2.61 (m,
2H), 2.34 (s, 1H), 2.07 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼159.3,134.6,127.0,113.8, 80.8, 72.0, 70.9, 55.3, 29.4; EIMS (m/z, %)
176 (Mþ), 137, 122, 109, 94, 77, 51, 39.
4.3.3. 1-(2-Methoxyphenyl)but-3-yn-1-ol 3c. Colorless oil,16b IR
(n
/cmꢀ1): 3427, 3294, 3069, 2940, 2118,1953,1597,1491,1462,1242,
1051, 864, 757, 638; 1H NMR (400 MHz, CDCl3):
d
¼7.42–7.25 (m,
2H), 7.00–6.87 (m, 2H), 5.08 (q, J¼7.2 Hz, 1H), 3.86 (s, 3H), 2.87 (s,
1H), 2.80–2.60 (m, 2H), 2.04 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz,
CDCl3):
d
¼156.2, 130.2, 128.8, 126.8, 120.7, 110.3, 81.3, 70.4, 69.0,
55.2, 27.4; EIMS (m/z, %) 176 (Mþ), 137, 121, 107, 94, 77, 51, 39.
4. Experimental
4.3.4. 1-(3-Methoxyphenyl)but-3-yn-1-ol 3d. Colorless oil,19 IR
4.1. General remarks
(n
/cmꢀ1): 3424, 3290, 3053, 2915, 2118,1952,1599,1487,1460,1261,
1154, 1043, 864, 787, 699, 647; 1H NMR (400 MHz, CDCl3):
d
¼7.29–
1H NMR spectra were recorded on a Brucker AM 400 MHz and
Brucker AC-E 200 MHz spectrometers in CDCl3 with TMS as an
internal standard. 13C NMR spectra were obtained on a Brucker AM-
400 operating at 100 MHz or a Brucker AC-E 200 operating at
50 MHz. IR spectra were recorded on an Alpha Centauri FI-IR
spectrometer. Mass spectra were recorded on an HP 5988A and GC/
MS/DS instruments. Elemental analyses were carried out on Carlo
Erba-1106 instruments. Purification of products was performed via
flash chromatography with 200–400 mesh silica gel (15:1 petro-
leum–diethyl ether). All substrates and reagents were obtained
commercially, which were prepared by standard procedures.
6.83 (m, 4H), 4.85 (t, J¼6.4 Hz, 1H), 3.80 (s, 3H), 2.65–2.62 (m, 2H),
2.42 (s, 1H). 2.09 (t, J¼2.4 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼159.7, 144.1, 129.5, 118.0, 113.4, 111.2, 80.6, 72.2, 71.0, 55.2, 29.4;
EIMS (m/z, %) 176 (Mþ), 137, 122, 109, 94, 77, 51, 39.
4.3.5. 1-(2,4-Dichlorophenyl)but-3-yn-1-ol 3e. White solid, mp
50–51 ꢁC,16b 48–49 ꢁC, IR ( /cmꢀ1): 3297, 2930, 2117,1912,1645,1589,
n
1472, 1385, 1043, 862, 820; 1H NMR (400 MHz, CDCl3):
d
¼7.58–7.26
(m, 3H), 5.23 (q, J¼6.4 Hz, 1H), 2.86–2.76 (m, 1H), 2.56–2.49 (m, 2H),
2.11 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼138.3, 134.0,
d
132.2,129.1,128.1,127.4, 79.8, 71.5, 68.3, 27.7; EIMS (m/z, %): 214 (Mþ),
179, 175, 145, 141, 105, 77, 51, 39.
4.2. Typical experimental procedure for the synthesis of
homopropargyl alcohols
4.3.6. 1-(2,6-Dichlorophenyl)but-3-yn-1-ol 3f. Colorless oil, IR
(n
/cmꢀ1): 3300, 2922, 2120, 1866, 1648, 1562, 1434, 1049, 778, 730,
Zn–Cu couple (324 mg) was placed in a flame dried round-
bottom flask (50 mL) fitted with magnetic bar. Then carbonyl
compounds (2 mmol) and propargyl bromide (3 mmol) were
643; 1H NMR (400 MHz, CDCl3):
2.8 Hz, 1H), 3.13–3.06 (m, 2H), 2.87 (q, J¼6.4, 2.4 Hz, 1H), 2.03 (t,
d
¼7.33–7.17 (m, 3H), 5.66 (q, J¼6.4,
J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼135.9, 134.5, 129.4,
d

X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
8687
129.4, 79.8, 70.6, 70.2, 25.3; EIMS (m/z, %): 179, 175 (Mþꢀ39), 147,
111, 77, 51, 39. Anal. Calcd for C10H8OCl2: C, 55.85; H, 3.75. Found: C,
56.07; H, 3.73.
(t, J¼6.0 Hz, 1H), 2.78 (q, J¼6.0, 2.8 Hz, 2H), 2.39 (s, 1H), 2.08 (t,
J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼154.6, 142.3, 110.2,
d
106.6, 79.8, 71.2, 66.1, 26.1; EIMS (m/z, %): 136 (Mþ), 119, 97, 79, 69,
51, 41, 39.
4.3.7. 1-(2-Chlorophenyl)but-3-yn-1-ol 3g. Colorless oil,20a IR
(n
/cmꢀ1): 3399, 3298, 3068, 2920, 2120, 1957, 1624, 1595, 1472,
4.3.15. 1-(Thiophen-2-yl)but-3-yn-1-ol 3o. Pale yellow oil,3 IR (
cmꢀ1): 3393, 3293, 3107, 2919, 2119, 1955, 1646, 1039, 853, 705,
646; 1H NMR (400 MHz, CDCl3):
¼7.28–7.26 (m, 1H), 7.05–6.94 (m,
n/
1439, 1040, 864, 757, 643; 1H NMR (400 MHz, CDCl3):
d¼7.64–7.22
(m, 4H), 5.28 (q, J¼6.4 Hz, 1H), 2.84–2.79 (m, 2H), 2.54 (s, 1H), 2.11
d
(t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼139.6, 131.6, 129.4,
2H), 5.12 (q, J¼6.4 Hz, 1H), 2.76 (q, J¼6.8, 2.8 Hz, 2H), 2.51 (s, 1H),
128.9, 127.1, 127.0, 80.3, 71.2, 68.7, 27.7; EIMS (m/z, %): 182, 180
2.11 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼146.1, 126.7,
d
(Mþ), 141, 113, 77, 51, 39.
125.0, 124.1, 80.0, 71.5, 68.5, 29.5; EIMS (m/z, %): 152 (Mþ), 134, 113,
85, 45, 39.
4.3.8. 1-(3-Chlorophenyl)but-3-yn-1-ol 3h. Colorless oil, IR
(n
/cmꢀ1): 3390, 3298, 3067, 2913, 2120, 1946, 1694, 1576, 1476,
4.3.16. (E)-1-Phenylhex-1-en-5-yn-3-ol 3p. Pale yellow oil,22 IR
1428, 1056, 885, 788, 692; 1H NMR (400 MHz, CDCl3):
d
¼7.45–7.26
(n
/cmꢀ1): 3389, 3295, 3029, 2913, 2119, 1953, 1600, 1495, 1445, 1101,
(m, 4H), 4.86 (q, J¼6.4 Hz, 1H), 2.69–2.57 (m, 2H), 2.44 (s, 1H), 2.09
1037, 969, 751, 692, 645; 1H NMR (400 MHz, CDCl3):
d
¼7.41–7.21 (m,
(t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼144.4, 134.4, 129.7,
5H), 6.67 (d, J¼16.4 Hz, 1H), 6.28 (dd, J¼16.4, 6.4 Hz, 1H), 4.48 (q,
128.1, 126.0, 123.9, 80.1, 71.6, 71.4, 29.5; EIMS (m/z, %): 181 (Mþþ1),
141, 113, 77, 51, 39. Anal. Calcd for C10H9OCl: C, 66.49; H, 5.02.
Found: C, 66.28; H, 5.00.
J¼6.4 Hz,1H), 2.62–2.50 (m, 2H), 2.18 (s,1H), 2.09(t, J¼2.8 Hz,1H); 13C
NMR (100 MHz, CDCl3):
d¼136.3,131.3,129.9,128.6,127.9,126.6, 80.2,
71.1, 70.7, 27.7; EIMS (m/z, %): 172 (Mþ), 133, 115, 105, 91, 77, 55, 39.
4.3.9. 1-(4-Chlorophenyl)but-3-yn-1-ol 3i. Colorless oil,20 IR
4.3.17. (E)-2-Methyl-1-phenylhex-1-en-5-yn-3-ol 3q. Pale yellow
(n
/cmꢀ1): 3392, 3298, 3062, 2913, 2120, 1955, 1902, 1650, 1598,
oil,16b IR ( /cmꢀ1): 3394, 3296, 3025, 2923, 2118, 1953, 1655, 1596,
n
1491, 1413, 1057, 866, 829, 644; 1H NMR (400 MHz, CDCl3):
d¼7.34–
1562,1493,1445,1019, 870, 749, 699, 644; 1H NMR (400 MHz, CDCl3):
7.26 (m, 4H), 4.85 (t, J¼6.4 Hz, 1H), 2.63–2.58 (m, 2H), 2.43 (s, 1H),
d
¼7.36–7.21 (m, 5H), 6.60 (s,1H), 4.37 (t, J¼6.4 Hz,1H), 2.59–2.57 (m,
2.08 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼140.8, 133.7,
2H), 2.15 (s,1H), 2.09 (t, J¼2.8 Hz,1H),1.89 (s, 3H); 13C NMR (100 MHz,
128.6, 127.2, 80.2, 71.6, 71.3, 29.5; EIMS (m/z, %): 180 (Mþ), 165, 163,
CDCl3):
d¼138.0, 137.2, 129.0, 128.1, 126.6, 126.5, 80.6, 75.5, 70.9, 26.1,
141, 113, 77, 51, 39.
13.5; EIMS (m/z, %): 186 (Mþ), 171, 147, 129, 115, 91, 77, 69, 55, 39.
4.3.10. 1-(3-Bromophenyl)but-3-yn-1-ol 3j. Colorless oil,20b IR (
cmꢀ1): 3393, 3296, 3063, 2912, 2119, 1952, 1642, 1569, 1424, 1061,
883, 785, 648; 1H NMR (400 MHz, CDCl3):
¼7.57–7.21 (m, 4H), 4.85
(q, J¼6.8 Hz, 1H), 2.67–2.62 (m, 2H), 2.43 (s, 1H), 2.10 (t, J¼2.4 Hz,
n/
4.3.18. (Z)-2-Bromo-1-phenylhex-1-en-5-yn-3-ol 3r. Colorless oil,16b
IR (
1043, 923, 864, 755, 694, 645; 1H NMR (400 MHz, CDCl3):
n
/cmꢀ1): 3393, 3296, 3027, 2918, 2120, 1955, 1641, 1492, 1443,
d
d
¼7.62–
7.26 (m, 5H), 7.18 (s,1H), 4.49 (q, J¼6.0 Hz,1H), 2.80–268 (m, 2H), 2.47
1H); 13C NMR (100 MHz, CDCl3):
d
¼144.6, 131.0, 130.0, 128.9, 124.4,
(s, 1H), 2.11 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
¼134.8,
d
122.6, 80.0, 71.6, 71.4, 29.5; EIMS (m/z, %): 226, 224 (Mþ), 209, 207,
185, 157, 77, 63, 51, 39.
129.2, 129.1, 128.3, 128.2, 127.0, 79.4, 75.5, 71.6, 26.6; EIMS (m/z, %):
252, 250 (Mþ), 213, 211, 195, 193, 171, 131, 115, 103, 89, 77, 63, 51, 39.
4.3.11. 1-(4-Bromophenyl)but-3-yn-1-ol 3k. Colorless oil,20a IR (
cmꢀ1): 3391, 3296, 3061, 2912, 2119, 1903, 1593, 1487, 1404, 1065,
1009, 866, 825, 646; 1H NMR (400 MHz, CDCl3):
n
/
4.3.19. (E)-1-(4-Methoxyphenyl)hex-1-en-5-yn-3-ol 3s. Pale yellow
oil, IR (
n
/cmꢀ1): 3400, 3291, 3005, 2932, 2118, 2015, 1830, 1651,
d
¼7.50–7.44 (m,
1607, 1513, 1460, 1033, 847, 813, 644; 1H NMR (400 MHz, CDCl3):
2H), 7.29–7.22 (m, 2H), 4.85 (q, J¼6.4 Hz, 1H), 2.67–2.56 (m, 2H),
d
¼7.35–7.26 (m, 2H), 6.90–6.80 (m, 2H), 6.60 (d, J¼16 Hz, 1H), 6.18–
2.39 (s, 1H), 2.08 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
6.12 (m,1H), 4.45 (q, J¼6.0 Hz,1H), 3.85–3.76 (m, 3H), 2.61–2.49 (m,
d
¼141.3, 131.6, 127.5, 121.8, 80.1, 71.6, 71.4, 29.4; EIMS (m/z, %): 226,
2H), 2.18 (s, 1H), 2.09 (t, J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
224 (Mþ), 209, 185, 157, 145, 128, 105, 89, 77, 63, 51, 39.
d
¼159.4, 130.9, 129.0, 127.8, 127.7, 114.0, 80.4, 71.0, 70.9, 55.3, 27.8;
EIMS (m/z, %): 202 (Mþ), 163, 145, 135, 121, 91, 77, 55, 39. Anal. Calcd
4.3.12. 1-(2-Bromophenyl)but-3-yn-1-ol 3l. Colorless oil, IR
(
n
/
for C13H14O2: C, 77.20; H, 6.98. Found: C, 77.07; H, 6.97.
cmꢀ1): 3395, 3297, 3065, 2919, 2120, 1952, 1648, 1565, 1519, 1467,
1434, 1024, 863, 755, 644; 1H NMR (400 MHz, CDCl3):
d
¼7.63–7.14
4.3.20. Dec-1-yn-4-ol 3t. Colorless oil,23 IR (
2928, 2858, 2119, 1649, 1460, 1048, 850, 633; 1H NMR (400 MHz,
CDCl3):
¼3.78–3.75 (m, 1H), 2.47–2.29 (m, 2H), 2.07–1.91 (m, 2H),
1.61 (s, 1H), 1.57–1.29 (m, 9H); 13C NMR (100 MHz, CDCl3):
n
/cmꢀ1): 3387, 3310,
(m, 4H), 5. 23 (q, J¼6.8 Hz, 1H), 2.84 (d, J¼2.8 Hz, 1H), 2.57–2.50 (m,
2H), 2.11 (t, J¼2.4 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d¼141.1,
d
132.6, 129.3, 127.7, 127.3, 121.7, 80.2, 71.2, 70.9, 27.7; EIMS (m/z, %):
226, 224 (Mþ), 209, 207, 185, 157, 77, 63, 51, 39. Anal. Calcd for
C10H9OBr: C, 53.36; H, 4.03. Found: C, 53.28; H, 4.00.
d
¼80.9,
70.8, 69.9, 36.2, 31.8, 29.2, 27.3, 25.5, 22.6, 14.1; EIMS (m/z, %): 139
(Mþꢀ15), 125, 115, 97, 81, 69, 55, 39.
4.3.13. 1-(Anthracen-9-yl)but-3-yn-1-ol 3m. Colorless oil,21 IR (
cmꢀ1): 3429, 3296, 3053, 2955, 2926, 2119, 1952, 1666, 1587, 1528,
1449, 1070, 957, 889, 735, 638; 1H NMR (400 MHz, CDCl3):
n
/
4.3.21. 2-Phenylpent-4-yn-2-ol 5a. Colorless oil,12o IR (
n
/cmꢀ1):
3433, 3294, 3061, 2979, 2118, 1956, 1603, 1494, 1100, 946, 852, 765,
d
¼8.45–
643; 1H NMR (400 MHz, CDCl3)
d
¼7.50–7.26 (m, 5H), 2.80–2.67 (m,
8.36 (m, 2H), 8.17 (s, 1H), 7.80–7.78 (m, 2H), 7.36–7.27 (m, 4H), 6.20
2H), 2.39 (s, 1H), 2.05 (t, J¼2.8 Hz, 1H), 1.65 (s, 3H); 13C NMR
(q, J¼6.8, 2.8 Hz, 1H), 3.17–3.04 (m, 2H), 2.75–2.68 (m, 1H), 1.97 (t,
(100 MHz, CDCl3)
d¼146.3, 128.2, 127.1, 124.7, 80.4, 73.2, 71.7, 34.6,
J¼2.8 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d
¼132.1, 131.3, 129.1,
29.2; EIMS (m/z, %) 159 (MþꢀH), 121, 105, 77, 51, 43, 39.
129.0, 128.4, 125.6, 125.5, 124.5, 81.3, 70.8, 69.1, 27.3; EIMS (m/z, %):
246 (Mþ), 229, 207, 189, 178, 151, 89, 74, 59, 45, 39.
4.3.22. 3-Phenylhex-5-yn-3-ol 5b. Colorless oil,12o IR /cmꢀ1):
(n
3463, 3296, 3061, 2971, 2932, 2117, 1955, 1604, 1493, 1131, 987, 762,
701, 644; 1H NMR (400 MHz, CDCl3)
¼7.44–7.25 (m, 5H), 2.81–2.69
(m, 2H), 2.33 (s, 1H), 2.03 (t, J¼2.8 Hz, 1H), 2.01–1.88 (m, 2H), 0.77
(t, 3H); 13C NMR (100 MHz, CDCl3)
¼144.5,128.1, 126.9, 125.3, 80.3,
4.3.14. 1-(Furan-2-yl)but-3-yn-1-ol 3n. Pale yellow oil,3 IR
cmꢀ1): 3383, 3295, 2918, 2121,1618,1503,1054,1015, 816, 744, 650;
1H NMR (400 MHz, CDCl3):
¼7.40 (d, 1H), 6.36–6.34 (m, 2H), 4.89
(n
/
d
d
d

8688
X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
75.7, 71.8, 34.3, 33.1, 7.98; EIMS (m/z, %) 174 (Mþ), 145, 135, 115, 105,
91, 77, 57, 51, 39.
(100 MHz, CDCl3)
d
¼155.8, 151.6, 106.0, 105.9, 80.0, 71.5, 70.0, 32.1,
26.1, 13.6; EIMS (m/z, %) 164 (Mþ), 125, 109, 53, 43, 39. Anal. Calcd
for C10H12O2: C, 73.15; H, 7.37. Found: C, 73.05; H, 7.33.
4.3.23. 2-(4-Bromophenyl)pent-4-yn-2-ol 5c. Colorless oil,12o IR (
cmꢀ1): 3440, 3296, 3063, 2978, 2926, 2118, 1954, 1649, 1487, 1395,
1085, 1008, 946, 824, 645; 1H NMR (400 MHz, CDCl3)
n/
4.3.31. (E)-3-Methyl-1-(thiophen-2-yl)hex-1-en-5-yn-3-ol 5k. Pale
d
¼7.52–7.48
yellow oil, IR (
1649, 1592, 1520, 1424, 1114, 1043, 961, 855, 814, 644; 1H NMR
(400 MHz, CDCl3)
n
/cmꢀ1): 3422, 3297, 3106, 2976, 2928, 2118, 1796,
(m, 2H), 7.40–7.28 (m, 2H), 2.74–2.70 (m, 2H), 2.41 (s, 1H), 2.08 (t,
J¼2.8 Hz, 1H), 1.65–1.60 (m, 3H); 13C NMR (100 MHz, CDCl3)
d
¼7.17–7.15 (m, 1H), 6.98–6.95 (m, 2H), 6.82 (d,
d
¼145.3, 131.3, 126.7, 121.1, 79.9, 73.0, 72.1, 34.5, 29.2; EIMS (m/z, %)
J¼3.6 Hz, 1H), 6.17 (d, J¼3.6 Hz, 1H), 2.54–2.53 (m, 2H), 2.17(s, 1H),
238 (Mþ), 199, 183, 155, 105, 91, 77, 43, 39.
2.12 (t, J¼2.8 Hz, 1H), 1.47 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
¼141.8, 134.1, 127.4, 126.0, 124.3, 121.7, 80.0, 71.8, 71.7, 33.3, 27.4;
4.3.24. 2-(4-Chlorophenyl)pent-4-yn-2-ol 5d. Colorless oil,12o IR (
n/
EIMS (m/z, %) 192 (Mþ), 153, 135, 109, 91, 69, 43, 39. Anal. Calcd for
cmꢀ1): 3437, 3299, 3064, 2978, 2928, 2119,1492,1093, 828, 750, 644;
C11H12OS: C, 68.72; H, 6.29. Found: C, 68.69; H, 6.28.
1H NMR (400 MHz, CDCl3)
2.76–2.39(m,2H), 2.17(s,1H), 2.06(t, J¼2.8 Hz,1H),1.64–1.57(m, 3H);
13C NMR (100 MHz, CDCl3)
¼144.8, 132.9, 128.3, 126.3, 79.9, 72.9,
72.0, 34.5, 29.2; EIMS (m/z, %) 194 (Mþ), 155, 139, 111, 75, 51, 43, 39.
d¼7.44–7.40 (m, 2H), 7.34–7.26 (m, 2H),
4.3.32. 2-(2,5-Dimethylthiophen-3-yl)pent-4-yn-2-ol 5l. Pale yel-
d
low oil, IR (
1553, 1481, 1448, 1142, 1113, 1033, 942, 829, 792, 640; 1H NMR
(400 MHz, CDCl3)
¼6.57 (s, 1H), 2.81–2.62 (m, 2H), 2.54–2.41 (m,
3H), 2.37–2.29 (m, 3H), 2.28 (s, 1H), 2.08 (t, J¼2.8 Hz, 1H), 1.64–1.55
n
/cmꢀ1): 3435, 3294, 3069, 2974, 2921, 2118, 1956, 1659,
d
4.3.25. 2-p-Tolylpent-4-yn-2-ol 5e. Colorless oil,3 IR ( /cmꢀ1): 3435,
n
3295, 3026, 2978, 2925, 2870, 2118, 1956, 1514, 1450, 1095, 944,
855, 818, 722, 642; 1H NMR (400 MHz, CDCl3)
¼7.40–7.36 (m, 2H),
7.26–7.16 (m, 2H), 2.78–2.65 (m, 2H), 2.37 (s, 1H), 2.05 (t, J¼2.8 Hz,
(m, 3H); 13C NMR (100 MHz, CDCl3)
d
¼140.7, 134.5, 132.4, 125.4,
d
80.6, 73.0, 71.6, 34.0, 28.7, 15.1, 14.9; EIMS (m/z, %) 194 (Mþ), 155,
139, 113, 77, 67, 59, 43, 39. Anal. Calcd for C11H14OS: C, 68.00; H,
7.26. Found: C, 67.89; H, 7.24.
1H), 1.65–1.58 (m, 3H); 13C NMR (100 MHz, CDCl3)
d
¼143.4, 136.7,
128.9, 124.6, 80.5, 73.1, 71.6, 34.5, 29.3, 21.0; EIMS (m/z, %) 174 (Mþ),
135, 119, 105, 91, 77, 65, 43, 39.
4.3.33. 4-Ethyloct-1-yn-4-ol 5m. Colorless oil, IR (
3308, 2959, 2936, 2869, 2118, 1956, 1649, 1460, 1138, 981, 633; 1H
NMR (400 MHz, CDCl3)
¼2.36–2.35 (m, 2H), 2.05 (t, J¼2.8 Hz, 1H),
1.60 (s, 1H),1.59–1.52 (m, 4H),1.36–1.27 (m, 4H), 0.94–0.87 (m, 6H);
n
/cmꢀ1): 3446,
4.3.26. 1,1-Diphenylbut-3-yn-1-ol and 1,1-diphenylbuta-2,3-dien-1-
d
ol 5fþ6f. Colorless oil,12o IR (
n
/cmꢀ1): 3463, 3293, 3030, 2922, 2854,
2118, 1957, 1492, 1447, 1168, 1051, 758, 700, 655; 1H NMR (400 MHz,
13C NMR (100 MHz, CDCl3)
d
¼80.8, 73.6, 71.1, 37.8, 31.1, 29.7, 25.7,
CDCl3)
2H), 3.16 (t, J¼2.8 Hz, 2H), 2.95 (s, 1H), 2.62 (s, 1H), 2.04 (t, J¼2.8 Hz,
1H); 13C NMR (100 MHz, CDCl3)
¼145.4, 128.2, 127.3, 126.1, 80.4,
80.2, 72.5, 33.3; EIMS (m/z, %) 222 (Mþ), 205,183,165,105, 77, 51, 39.
d¼7.46–7.23 (m,10H), 5.95 (t, J¼6.4 Hz,1H), 4.98 (d, J¼6.4 Hz,
23.2, 14.1, 7.93; EIMS (m/z, %) 115 (Mþꢀ39), 97, 85, 59, 57, 55, 43, 39.
Anal. Calcd for C10H18O: C, 77.87; H, 11.76. Found: C, 77.69; H, 11.73.
d
4.3.34. 4-Methylnon-1-yn-4-ol 5n. Colorless oil,24 IR
(n
/cmꢀ1):
3407, 3308, 2934, 2864, 2118, 1956, 1460, 1376, 1148, 918, 770, 633;
4.3.27. 2-(Naphthalen-6-yl)pent-4-yn-2-ol 5g. Colorless oil,12o IR (
cmꢀ1): 3433, 3295, 3057, 2929, 2118, 1954, 1600, 1506, 1455, 1123,
943, 858, 749, 642; 1H NMR (400 MHz, CDCl3)
¼7.96–7.81 (m, 4H),
7.58–7.44 (m, 3H), 2.89–2.76 (m, 2H), 2.55 (s, 1H), 2.04 (t, J¼2.8 Hz,
1H), 1.74–1.69 (m, 3H); 13C NMR (100 MHz, CDCl3)
n
/
1H NMR (400 MHz, CDCl3)
d
¼2.37 (t, J¼2.8 Hz, 2H), 2.08 (t,
J¼2.8 Hz,1H), 1.77 (s,1H),1.61–1.25 (m, 11H), 0.92–0.88 (m, 3H); 13C
d
NMR (100 MHz, CDCl3)
d
¼80.9, 71.7, 71.2, 41.1, 32.4, 32.2, 26.2, 23.6,
22.6, 14.0; EIMS (m/z, %) 154 (Mþ), 115, 99, 83, 71, 55, 43, 39.
d
¼143.6, 133.1,
132.4, 128.2, 128.0, 127.5, 126.1, 125.9, 123.31, 123.2, 80.3, 73.4, 71.9,
4.3.35. 1-(Prop-2-ynyl)cyclohexanol 5o. Colorless oil,12o IR
(n/
34.5, 29.2; EIMS (m/z, %) 210 (Mþ), 171, 155, 127, 77, 63, 51, 43, 39.
cmꢀ1): 3347, 3290, 2972, 2932, 2116, 1956, 1458, 1180, 1032, 945,
833, 725, 642; 1H NMR (400 MHz, CDCl3)
d
¼2.38–2.34 (m, 2H), 2.08
4.3.28. 2-(4-Biphenyl)pent-4-yn-2-ol 5h. White solid, mp 32–33 ꢁC,
(t, J¼2.8 Hz,1H),1.76 (s,1H),1.69–1.25 (m,10H); 13C NMR (100 MHz,
IR (
n
/cmꢀ1): 3437, 3293, 3057, 2977, 2926, 2118, 1955, 1602, 1560,
CDCl3)
d¼80.6, 71.4, 70.3, 36.7, 32.8, 25.5, 22.5; EIMS (m/z, %) 137
1487, 1450, 1183, 1095, 943, 840, 767, 643; 1H NMR (400 MHz,
(Mþ-H), 99, 81, 69, 55, 39.
CDCl3)
d
¼7.60–7.34 (m, 9H), 2.84–2.71 (m, 2H), 2.43 (s, 1H), 2.08 (t,
J¼2.8 Hz, 1H), 1.68 (s, 3H); 13C NMR (100 MHz, CDCl3)
d¼145.3,
4.3.36. 1-(Prop-2-ynyl)cyclohex-2-enol 5p. Colorless oil,25 IR (
n/
140.7, 140.0, 128.8, 127.3, 127.1, 127.0, 125.2, 80.4, 73.1, 71.9, 34.6,
29.2; EIMS (m/z, %) 236 (Mþ), 197, 152, 115, 43, 39. Anal. Calcd for
C17H16O: C, 86.41; H, 6.82. Found: C, 86.37; H, 6.80.
cmꢀ1): 3404, 3301, 3022, 2936, 2117, 1656, 1433, 1170, 1078, 988,
853, 734, 638; 1H NMR (400 MHz, CDCl3)
d
¼5.91–5.86 (m, 1H),
5.74–5.72 (m, 1H), 2.45–2.44 (m, 2H), 2.09–1.62 (m, 8H); 13C NMR
(100 MHz, CDCl3)
d
¼131.1, 130.8, 80.4, 71.1, 68.5, 35.2, 32.6, 25.1,
4.3.29. 2-(9H-Fluoren-7-yl)pent-4-yn-2-ol 5i. White solid, mp 82–
19.0; EIMS (m/z, %) 136 (Mþ), 97, 79, 68, 55, 41, 39.
83 ꢁC, IR ( /cmꢀ1): 3463, 3277, 3055, 2971, 2923, 2115, 1948, 1651,
n
1589, 1453, 1121, 1083, 951, 833, 770, 643; 1H NMR (400 MHz,
Acknowledgements
CDCl3)
d
¼7.78–7.69 (m, 3H), 7.55–7.25 (m, 4H), 3.90 (s, 2H), 2.85–
2.72 (m, 2H), 2.46 (s, 1H), 2.07 (t, J¼2.8 Hz, 1H), 1.70 (s, 3H); 13C
The work was supported by the Natural Science Foundation of
China (Grant 20272047, 20572086), the Gansu Natural Science
Foundation of China (0308RJZA-100) and Key Laboratory of Eco-
Environment-Related Polymer Material (Northwest Normal Uni-
versity), Ministry of the Education of China.
NMR (100 MHz, CDCl3)
d
¼145.0, 143.4, 143.3, 141.3, 140.7, 126.7,
126.6, 125.0, 123.4, 121.5, 119.9, 119.5, 80.5, 73.5, 71.8, 37.0, 34.8,
29.4; EIMS (m/z, %) 248 (Mþ), 209, 193, 165, 152, 115, 43, 39. Anal.
Calcd for C18H16O: C, 87.06; H, 6.49. Found: C, 86.89; H, 6.47.
4.3.30. 2-(5-Methylfuran-2-yl)pent-4-yn-2-ol 5j. Pale yellow oil, IR
(n
/cmꢀ1): 3417, 3297, 2984, 2923, 2120, 1958, 1663, 1561, 1517, 1450,
References and notes
1108, 1023, 938, 787, 642; 1H NMR (400 MHz, CDCl3)
d¼6.17–6.15
1. (a) Yanagisawa, A.; Habaue, S.; Yamamoto, H. J. Org. Chem. 1989, 54, 5198–5200;
(b) Nicolaou, K. C.; Skokotas, G.; Furuya, S.; Suemune, H.; Nicolaou, D. C. Angew.
Chem., Int. Ed. Engl. 1990, 29, 1064–1067; (c) Fryhle, C. B.; Williard, P. G.; Rybak,
(m, 1H), 5.91–5.89 (m, 1H), 2.86–2.67 (m, 2H), 2.44–2.40 (m, 3H),
2.28 (s, 1H), 2.09–2.07 (m, 1H), 1.65–1.60 (m, 3H); 13C NMR

X. Ma et al. / Tetrahedron 65 (2009) 8683–8689
8689
C. M. Tetrahedron Lett. 1992, 33, 2327–2330; (d) Hirama, M.; Tokuda, M.; Fuji-
wara, K. Synlett 1991, 651–653; (e) Lee, A. S.-Y.; Cheng, R.-Y.; Pan, O.-G. Tetra-
hedron Lett. 1997, 38, 443–446.
2. (a) Gu, C.-Z.; Li, Q.-R.; Yin, H. Chin. Chem. Lett. 2005, 16, 1573–1576; (b) Li, Q.-R.;
Gu, C.-Z.; Yin, H. Chin. J. Chem. 2006, 24, 72–78; (c) Isaac, M. B.; Chan, T. H.
J. Chem. Soc., Chem. Commun. 1995, 1003–1004; (d) Kwon, J. S.; Pae, A. N.; Choi,
K. I.; Koh, H. Y.; Kim, Y.; Cho, Y. S. Tetrahedron Lett. 2001, 42, 1957–1959; (e) Wu,
S.-H.; Huang, B.-Z.; Gao, X. Synth. Commun. 1990, 20, 1279–1286.
Tetrahedron Lett. 2006, 47, 5173–5176; (l) Lee, K.-C.; Lin, M.-J.; Loh, T.-P. Chem.
Commun. 2004, 2456–2457; (m) Loh, T.-P.; Lin, M.-J.; Tan, K.-L. Tetrahedron Lett. 2003,
44, 507–509; (n) Yananisawa, A.; Okitsu, S.; Arai, T. Synlett 2005,1679–1682; (o) Li, Z.;
Jia, Y.; Zhou, J.-Y. Synth. Commun. 2000, 2515–2524; (p) Cabezas, J. A.; Alvarez, L. X.
Tetrahedron Lett. 1998, 39, 3935–3938.
13. Sharifi, A.; Abaee, M. S.; Mirzaei, M.; Abedi, V. Arkivoc 2006, 17–21.
14. (a) Hauser, F. M.; Philip, A.; Carroll, F. I. J. Org. Chem. 1973, 38, 3693–3695;
(b) Stephenson, L. M.; Gemmer, R. V.; Current, S. P. J. Org. Chem. 1977, 42, 212–
214; (c) Santaniello, E.; Manzocchi, A. Synthesis 1977, 698–699.
15. Papadopoulou, M. V. Chem. Ber. 1989, 122, 2017–2018.
3. Lee, A. S.-Y.; Chu, S.-F.; Chang, Y.-T.; Wang, S.-H. Tetrahedron Lett. 2004, 45,
1551–1553.
4. Zhang, L.-J.; Mo, X.-S.; Huang, Y.-Z. J. Organomet. Chem. 1994, 471, 77–85.
5. Hojo, M.; Sakuragi, R.; Okabe, S.; Hosomi, A. Chem. Commun. 2001, 357–358.
6. (a) Araki, S.; Ito, H.; Butsugan, Y. J. Org. Chem. 1988, 53, 1833–1835; (b) Tanaka,
H.; Hamatani, T.; Yamashita, S.; Torii, S. Chem. Lett. 1986, 1461–1462.
7. Iseki, K.; Kuroki, Y.; Kobayashi, Y. Tetrahedron: Asymmetry 1998, 9, 2889–2894.
8. (a) Mukaiyama, T.; Harada, T. Chem. Lett. 1981, 621–629; (b) Nakagawa, T.;
Kasatkin, A.; Sato, F. Tetrahedron Lett. 1995, 36, 3207–3210.
16. (a) Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice; Oxford
University Press: New York, NY, 1997; (b) Wang, J.-X.; Jia, X.; Meng, T.; Xin, L.
Synthesis 2005, 2838–2844; (c) Bai, L.; Wang, J.-X.; Zhang, Y. Green Chem. 2003,
615–617; (d) Wei, Y.; Ren, H.; Wang, J.-X. Tetrahedron Lett. 2008, 49, 5697–5699;
(e) Bai, L.; Wang, J.-X. Adv. Synth. Catal. 2008, 350, 315–320; (f) Jia, X.; Li, H.;
Wang, J.-X.; Xin, L.; Meng, T. Chin. J. Synth. Chem. 2005, 13, 489–491; (g) Zhou,
W.; Yan, W.; Wang, J.-X.; Wang, K. Synlett 2008, 137–141.
9. Hojo, M.; Harada, H.; Ito, H.; Hosomi, A. Chem. Commun. 1997, 2077–2078.
10. Ishiguro, M.; Ikeda, N.; Yamamoto, H. J. Org. Chem. 1982, 47, 2225–2227.
11. Lee, A. S.-Y.; Chang, Y.-T.; Wang, S.-H.; Chu, S.-F. Tetrahedron Lett. 2002, 43,
8489–8492.
17. Araki, S.; Ito, H.; Butsugan, Y. J. Organomet. Chem. 1988, 347, 5–8.
18. Michelot, D. Synth. Commun. 1989, 19, 1705–1711.
19. (a) Viola, A.; Proverb, R. J.; Yates, B. L.; Larrahondo, J. J. Am. Chem. Soc. 1973, 95,
3609–3613; (b) Shim, J.-G. J. Organomet. Chem. 1999, 588, 20–21.
20. (a) Iyoda, M.; Kanao, Y.; Nishizaki, M.; Oda, M. Bull. Chem. Soc. Jpn. 1989, 62,
3380–3382; (b) Zheng, Y.-F.; Bao, W.-L.; Zhang, Y.-M. Synth. Commun. 2000, 30,
3517–3520.
21. Hashmi, A. S. K.; Ruppert, T. L.; Kno¨fel, T.; Bats, J. W. J. Org. Chem. 1997, 62,
7295–7304.
22. Shao, Q.-Y.; Gao, X.; Sun, P.-D.; Wu, S.-H. Chin. J. Org. Chem. 1991, 11, 195–198.
23. James, A. M.; Wang, X.-J. J. Org. Chem. 1991, 56, 960–969.
24. Akio, N. Agric. Biol. Chem. 1969, 33, 225–229.
12. (a) Lee, P. H.; Kim, H.; Lee, K. Adv. Synth. Catal. 2005, 347, 1219–1222; (b) Kim, S.;
Lee, K.; Seomoon, D.; Lee, P. H. Adv. Synth. Catal. 2007, 349, 2449–2453; (c) Takeda,
T.; Ando, M.; Sugita, T.; Tsubouchi, A. Org. Lett. 2007, 9, 2875–2878; (d) Alouane, N.;
Vrancken, E.; Mangeney, P. Synthesis 2007, 1261–1264; (e) Vrancken, E.; Alouane,
N.; Gerard, H.; Mangeney, P. J. Org. Chem. 2007, 72, 1770–1779; (f) Arimitsu, S.;
Jacobsen, J. M.; Hammond, G. B. Tetrahedron Lett. 2007, 483, 1625–1627;
(g)Arimitsu, S.;Hammond, G. B. J. Org. Chem. 2006, 71, 8665–8668; (h) Masuyama,
Y.; Yamazaki, R.; Ohtsuka, M.; Kurusu, Y. Synlett 2006,1750–1752; (i) Schneider, U.;
Sugiura, M.; Kobayashi, S. Tetrahedron 2006, 62, 496–502; (j) Banerjee, M.; Roy, S.
Chem. Commun. 2003, 534–535; (k) Hirayama, L. C.; Dunham, K. K.; Singaram, B.
25. Haruta, J.-I.; Nishi, K.; Matsuda, S.; Akai, S.; Tamura, Y.; Kita, Y. J. Org. Chem.
1990, 55, 4853–4859.