Highly efficient water promoted allylation and propargylation of arylepoxides via rearrangement-carbonyl addition

Article abstract of DOI:10.1016/j.tet.2005.10.005

A simple and highly efficient one-pot procedure for allylation and propargylation of arylepoxides has been developed. A combination of SnCl ₂ and catalytic Pd(0) or Pd(II) promotes the reaction of organic halides and epoxides in DMSO with controlled water addition, leading to the regioselective formation of the corresponding homoallyl and homopropargyl alcohols in good yields.

Full text of DOI:10.1016/j.tet.2005.10.005

Tetrahedron 62 (2006) 678–683
Highly efficient water promoted allylation and propargylation
of arylepoxides via rearrangement-carbonyl addition
*
Ujjal Kanti Roy and Sujit Roy
Organometallics and Catalysis Laboratory, Chemistry Department, Indian Institute of Technology, Kharagpur 721302, India
Received 1 July 2005; revised 21 September 2005; accepted 6 October 2005
Available online 7 November 2005
Abstract—A simple and highly efficient one-pot procedure for allylation and propargylation of arylepoxides has been developed.
A combination of SnCl2 and catalytic Pd(0) or Pd(II) promotes the reaction of organic halides and epoxides in DMSO with controlled water
addition, leading to the regioselective formation of the corresponding homoallyl and homopropargyl alcohols in good yields.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
Sn(OTf)2 as the second additive.6 Remarkably, we now find
that the reactivity of organotin towards epoxides can be
tuned simply by the controlled addition of water in DMSO
leading to homoallyl and homopropargyl alcohols via
epoxide rearrangement-carbonyl addition reaction, and
present our findings in this report (Scheme 1).
The addition of allyl, propargyl or allenylstannanes to
organic electrophiles like aldehydes, imines, and epoxides is
a well-known tool for carbon–carbon bond formation in
organic chemistry.1 Epoxides are one of the most useful and
versatile substrates in organic synthesis due to their high
reactivity. A number of methods have been reported for the
cleavage of epoxides with various nucleophiles. On the
other hand, only a few methods are known for the allylation
and propargylation of epoxides.2–4 Except for a few, the
methods suffer from a lack of efficiency and simplicity.
Therefore, the development of simple and novel reagents,
which are more efficient and provide convenient procedures
with improved yields still remains a challenge for synthetic
organic chemists.
O
R1
R2
Sn(II)/H2O
R6
R5
R7
Br
R3
R4
Br
OH R5
R4
Cat. Pd(0) Cat. Pd(II)
OH
6 R7
R1
R1
Along with others, we have been exploring a bimetallic
strategy to generate allyl and propargyl organometallic
reagents.5 The strategy involves oxidative addition of an
organic halide (RX) across catalytic d8/d10 metal [M],
followed by redox-transmetallation of R-[M]-X to tin(II) to
generate R-Sn(IV) in situ. Successful delineation of the
strategy for carbonyl allylation and propargylation
prompted us to investigate the nucleophilic addition of
organotin(IV) to an epoxide. Previously we reported that
under strictly anhydrous condition, lithium hydroxide could
promote such reactivity. However, a major synthetic
limitation was the use of stoichiometric excess (3 equiv
with respect to SnII) of lithium hydroxide, along with
R2
R3
R2
R
Scheme 1. Tandem epoxide rearrangement and allylation/propargylation.
2. Results and discussion
2.1. Effect of water and catalyst
Reaction of styrene oxide 2a and 3-bromopropene 1a in the
presence of anhydrous stannous chloride and catalytic
Pd2(dba)3$CHCl3 in DMSO at 60 8C led to the formation of
1-phenyl-pent-4-en-2-ol 3a in 39% yield (Table 1, entry 4).
The yield of 3a was negligible for reactions in DCM, and
THF, while in DMF it was 33%. On the other hand, reaction
in the absence of catalyst afforded majorly 1-phenyl-ethane-
1,2-diol 6, along with unreacted epoxide 2a and epoxide
rearrangement product, phenylacetaldehyde 7 (entry 5).
Keywords: Allylation; Propargylation; Organotin; Palladium; Aqueous
promotion.
Corresponding author. Tel.: C91 3222 283338; fax: C91 3222 282252;
e-mail: sroy@chem.iitkgp.ernet.in
*
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.10.005

U. K. Roy, S. Roy / Tetrahedron 62 (2006) 678–683
679
suggests that a likely active species is RSn(OH)3.7c This
suggestion is close in line with the one proposed by Li et al.
for the arylation of aldehydes.8 It is presumed that by virtue
of its coordinating ability DMSO could further stabilize the
hydroxytin(IV) intermediate.10
Table 1. Reaction of styrene epoxide with allyl bromide: effect of watera
Br
O
1a
OH
Ph
SnCl2, catalyst, solvent
2a
3a
#
Solvent
Water (ml)
Temperature (8C)
Yield (%)
Screening of catalysts at 2% loading (Table 2) indicates that
among the metal complexes, Pd2dba3$CHCl3 and NiCl2
(PPh3)2 cause O60% product formation, while among the
metal salts Pd(OAc)2 and Ni(OAc)2$4H2O are superior to
others. The best condition is shown as in entry 15.
1
2
3
4
5b
6
7
8
9
DCM
THF
—
—
—
—
—
70
70
70
70
40
60
60
60
60
60
40
60
60
Trace
Trace
33
39
Tracec
73
Trace
Trace
55
DMF
DMSO
DMSO
DMSO
DCM
THF
Table 2. Reaction of styrene epoxide with allyl bromide: effect of catalysta
DMF
Br
O
1a
a Condition: styrene oxide 0.5 mmol, SnCl2 1 mmol, allyl bromide 1.5 mmol,
Pd2dba3$CHCl3 0.01 mmol, solvent 3 ml, 11 h.
b Without catalyst.
OH
Ph
SnCl2, catalyst, solvent
2a
3a
c Major products PhCH(OH)CH2OH 6 and PhCH2CHO 7.
#
Catalyst
mol (%)
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
None
CuCl
—
30
24
24
24
11
11
11
11
11
11
11
11
11
11
11
Trace
27
33
47
55
64
50
43
49
54
55
59
60
73
Remarkably, the addition of a controlled amount of water
(w3 equiv) in DMSO dramatically increased the yield of 3a
to 73% (entry 6). Note that such dramatic enhancement is
not observed for other organic-aqueous combinations
(entries 7–9).
CuCl2,2H2O
Cu(OAc)2$H2O
Ni(OAc)2$4H2O
NiCl2(PPh3)2
PtCl2(PPh3)2
Pd(dba)2
30
2
2
2
2
2
2
2
2
2
2
2
The effect of water on the yield of homoallyl alcohol 3a and
diol 6 was further scrutinised carefully for reactions
conducted with 2 mmol of SnCl2. As shown in Figure 1,
upon slow addition of water the yield of 3a slowly increases
and reaches a maximum near 6–8 mmol, after which it
decreases sharply. On the other hand, the yield of diol 6
remains below 20% until 6–8 mmol of water is added;
beyond which it rises very rapidly. From data points for any
two successive addition of water, one finds that the yield
difference in case of 3a does not correlate linearly with that
of 6. The above observations highlight the critical role of
water in enhancing the nucleophilic addition reaction rate.
9
Pd(PPh3)4
10
11
12
13
15
PdCl2(PPh3)2
PdCl2(MeCN)2
PdCl2(Phen)
Pd(OAc)2
Pd2dba3$CHCl3
a Condition: styrene oxide 0.5 mmol, anhydrous SnCl2 1 mmol, allyl
bromide 1.5 mmol, DMSO 3 ml, H2O 70 ml, 60 8C.
2.2. Epoxide rearrangement-carbonyl allylation
The formation of homoallyl alcohol 3a suggests that the
reaction pathway does not involve direct allylation of the
epoxide, instead is a case of allylation of a benzylic
aldehyde. Lewis acid catalyzed rearrangement of epoxides
to benzylic aldehydes is well documented.11 Control
experiments with styrene oxide confirmed that under our
reaction conditions, such rearrangement is promoted by
tin(II) in DMSO, but not the transition metal partner. Thus,
reaction of 2a (0.5 mmol) with SnCl2 (0.3 mmol) in DMSO
resulted in rapid rearrangement within 30 min leading to the
formation of phenylacetaldehyde 7 (84%). Under similar
conditions, but with Pd2dba3$CHCl3 the yield of phenyl-
acetaldehyde 7 was negligible even after 6 h. Therefore, the
epoxide rearrangement is viewed as a typical Lewis acid
catalyzed pathway involving SnII (Scheme 2).12
80
70
3a
60
50
40
30
20
6
10
0
0
2
4
6
8
10 12 14 16
Sn II
Mmol of Water added
O
SnII
O
H
H
H
Figure 1. Effect of water on epoxide allylation. Homoallyl alcohol 3a (,),
diol 6 (B). Condition: styrene oxide 2a 1 mmol, SnCl2 2 mmol, allyl
bromide 3 mmol, Pd2dba3 2 mol%, DMSO 3 ml, 60 8C, 11 h.
Ar
Ar
Ar
Our findings on the role of water corroborates many recent
reports on the increased reactivity of in situ or ex situ
generated organometallic nucleophiles in aqueous or
aqueous-organic medium.7,8 It is now well established that
the reagent combination of Pd(0/II)/SnCl2/allyl bromide
generates allyltrihalostannane.9 That a stoichiometric
3 equiv of water with respect to tin is needed in our case
II
-
Sn
H
O
H
+
Ar
– SnII
O
H
Scheme 2. SnII assisted rearrangement of arylepoxide.

680
U. K. Roy, S. Roy / Tetrahedron 62 (2006) 678–683
2.3. Generality of the method: allylation of arylepoxide
yield (entries 2, 4, 6). Furthermore, 1-(9-anthryl)-ethylene
oxide 2c reacted smoothly with allyl bromide 1a giving rise
to the allylation product 3h in 83% yield (entry 8). For
reactions with 3-substituted allyl bromides, the syn/anti
diastereoselectivity in the product varied from case to case
(entries 2–6). In comparison to the very good allylation
reactivity of arylepoxides, attempted reactions with
aliphatic epoxides provided complicated mixtures. Thus,
reactions of cyclohexene oxide and 1a even at lower
temperature gave rise to a number of intractable products.
The generality of the reaction was further tested for the
allylation of epoxides (Table 3). Reaction of styrene
epoxide 2a with allyl bromides 1a–1e afforded exclusively
the g-regioselective products 3a, 3c, 3e, 3g, and 3i in
65–75% yields (entries 1, 3, 5, 7, 9). To test if steric
crowding is tolerated, a-methylstyrene epoxide 2b was
reacted with allyl bromides 1a, 1b, and 1c to afford the
corresponding homoallyl alcohols 3b, 3d, and 3f in 70–82%
Table 3. Epoxide rearrangement-allylationa
2.4. Generality of the method: propargylation
of arylepoxide
OH R5
R5
O
R1
R1
R2
R3
R4
Br
+
The scope of the reaction was successfully extended to the
propargylation of epoxides. In the presence of catalytic
Pd(OAc)2, the model reaction of 3-bromo-prop-1-yne 4a
and styrene oxide 2a yielded 68% of 1-phenyl-pent-4-yn-2-ol
5a (Table 4, entry 4). In comparison, other catalysts showed
poor efficiency. Complete absence of isomeric allenyl
alcohol suggests that under the reaction conditions,
metallotropic rearrangement between the propargyltin and
allenyltin is completely arrested.5f The generality of the
method was further tested for the reaction of styrene oxide
2a, a-methyl styrene oxide 2b and 1-(9-anthryl)-ethylene
oxide 2c with propargyl bromides 2a–2c affording moderate
to good yields of the corresponding homopropargyl alcohols
R4
R2
R3
3a - 3i
2
1
1a: R3=H, R4=H, R5=H
2a: R1=Ph, R2=H
2b: R1=Ph, R2=Me
2c: R1=Anthryl, R2=H
1b: R3=Me, R4=H, R5=H
1c: R3=nPr, R4=H, R5=H
1d: R3=Me, R4=Me, R5=H
1e: R3=H, R4=H, R5=Me
#
1
Bromide Epoxide
Product
Time Yield
(h)
syn/
antib
(%)
OH
Ph
Ph
1a
1a
2a
2b
11
73
—
3a
OH
Table 4. Reaction of styrene epoxide with propargyl bromide: effect of
catalysta
2
3
4
5
6
7
13
13
13
14
13
12
80
71
82
67
70
75
63/37
Me
3b
Br
O
4a
SnCl2,catalyst, solvent
Catalyst
OH
OH
Ph
2a
5a
Ph
Ph
1b
1b
1c
1c
1d
2a
2b
2a
2b
2a
40/60
80/20
66/34
70/30
—
Me
#
mol%
Yield (%)
3c
1
2
3
4
5
6
7
8
9
None
—
2
4
2
2
2
2
2
2
Trace
31
26
68
59
52
31
28
2
OH
NiCl2(PPh3)2
Ni(OAc)2$4H2O
Pd(OAc)2
PtCl2(PPh3)2
PdCl2(Phen)
Pd(PPh3)4
Me Me
3d
OH
Ph
Ph
Pd(dba)2
Pd2dba3$CHCl3
nPr
3e
a Condition: styrene oxide 0.5 mmol, SnCl2 1 mmol, propargyl bromide
1.5 mmol, catalyst 0.01 mmol, DMSO–H2O (3 ml–70 ml), rt, 20 h.
OH
nPr
Me
3f
5a–5e (Table 5).
OH
Ph
2.5. Comments on plausible mechanism
Me
3g
Me
Whilst a detailed mechanism of the present reaction must
await further studies, some of the plausible bond forming
steps are enumerated below (Scheme 3, where RZallyl or
propargyl). The suggestions are based on previous studies7–11
and observations described in previous sections. In early
stages of the reaction formation of organotrihalostannane
R-SnXCl2 I is postulated by a well-known redox trans-
metallation pathway involving oxidative addition of organic
halide RX across palladium, insertion of tin(II) halide,
followed by reductive elimination.9 The profound involve-
ment of water enables us to suggest the formation of a
OH
8
9
1a
1e
2c
2a
14
13
83
35
—
—
3h
Ph
OH
3i
a Condition: epoxide 0.5 mmol, SnCl2 1 mmol, allyl bromide 1.5 mmol,
Pd2dba3$CHCl3 0.01 mmol, DMSO–H2O (3 ml–70 ml), 60 8C.
b Based on NMR.

U. K. Roy, S. Roy / Tetrahedron 62 (2006) 678–683
681
Table 5. Epoxide rearrangement-propargylationa
organotin intermediate II to aldehyde III to furnish the
end-organic product.
OH
R6
R6
O
R1
R7
Br
R1
R2
+
R7
R2
2
4
3. Conclusion
5a-5e
2a: R1=Ph, R2= H
2b: R1=Ph, R2=Me
2c: R1=Anthryl, R2=H 4c: R7=Me, R7=Me
4a: R6=H, R7=H
4b: R6=Me, R7=H
In summary, we have demonstrated a facile allylation and
propargylation of arylepoxides to afford the corresponding
homoallyl and homopropargyl alcohols with a two carbon
extension. The reaction is promoted simply by the addition
of a limited amount of water to generate a reactive organotin
species. The end-organic product arises from simultaneous
epoxide rearrangement and carbonyl addition, the latter
being 100% g-regioselective, and devoid of allenyl-isomers
(in case of propargylation). All of the above features are
expected to add to the synthetic utility of the present
reaction. Further work is warranted to understand the
mechanistic details of the reaction.
#
1
Bromide Epoxide
Product
Time Yield
(h)
syn/
antib
(%)
OH
Ph
Ph
4a
4a
2a
2b
18
61
—
5a
OH
2
3
22
15
43
92
65/35
Me
5b
HO
4a
2c
—
4. Experimental
5c
4.1. General comments
OH
1H(200 MHz)NMRspectrawererecordedonaBRUKER-AC
200 spectrometer. Chemical shifts are reported in ppm from
tetramethylsilane with the solvent resonance as the internal
standard (deuterochloroform: d 7.27 ppm). Data are
reported as follows: chemical shifts, multiplicity (sZ
singlet; dZdoublet; tZtriplet; qZquartet; brZbroad;
mZmultiplet), coupling constant (Hz). 13C (54.6 MHz)
NMR spectra were recorded on a BRUKER-AC 200 MHz
spectrometer with complete proton decoupling. Chemical
shifts are reported in ppm from tetramethylsilane with the
solvent resonance as the internal standard (deuterochloro-
form: d 77.0 ppm). ESI mass spectra were recorded on a
Waters LCT mass spectrometer. Elemental analyses were
carried out using a CHNS/O Analyzer Perkin Elmer 2400
Series II instrument. IR spectra were taken on a Thermo
Nicolet FTIR Spectrometer (NEXUS-870). Melting points
were determined on an Electrothermal 9100 melting point
apparatus and are uncorrected.
Ph
Ph
4
5
4b
4c
2a
2a
14
16
71
48
40/60
—
Me
5d
OH
Me
5e
Me
a Condition: epoxide 0.5 mmol, SnCl2 1 mmol, propargyl bromide
1.5 mmol, Pd(OAc)2 0.01 mmol, solvent DMSO–H2O (3 ml–70 ml), rt.
b Based on NMR.
Step I: Activation of Organic Halide
SnCl2
- Pd0
R
R
PdII
R-X
Pd0
PdII
X
R-SnXCl2
(I)
SnXCl2
Step II: Activation of Organotin by Water
H2O
(I)
R-SnXn(OH)3-n
(II)
R-SnXCl2
4.2. General procedure
Step III: Activation of Aryl epoxide by SnII
The procedure given below was followed in all cases. All
products showed satisfactory spectral and analytical data.
SnII
O
(III)
ArCH2CHO
Ar
Step IV: Carbonyl Addition to Benzylic Aldehyde
OH
4.3. Allylation of epoxides
Pd2dba3$CHCl3 (10 mg, 0.01 mmol) was added to a
solution of allyl bromide (1.5 mmol) in a DMSO–H2O
solvent mixture (3 ml–70 ml) and was allowed to stir for
5 min at a bath temperature of 60 8C. Anhydrous SnCl2
(190 mg, 1 mmol) was added and the reaction stirred for 6 h.
Finally, epoxide (0.5 mmol) was added and the reaction was
monitored by TLC. After completion, the reaction was
quenched by adding water and ammonium fluoride. The
mixture was extracted into ethylacetate. The combined
organic layer was washed with water (4!50 ml), brine and
dried over anhydrous MgSO4. Solvent removal under
reduced pressure followed by column chromatography
(II)
Ar
ArCH2CHO
(III)
R
Scheme 3. Plausible mechanism for epoxide rearrangement and carbonyl
addition of reactive organotin.
more reactive organotin intermediate RSnXn(OH)3-n II in
solution.7,8 Under the reaction conditions, simultaneous
rearrangement of the arylepoxide to the benzylic aldehyde
III occurs (vide Scheme 2).12 The final step of the reaction
would involve a carbonyl addition via SE20 attack of

682
U. K. Roy, S. Roy / Tetrahedron 62 (2006) 678–683
over silica gel 60–120 (eluent, 2% EtOAc in hexane)
afforded the desired allylated product.
1262, 1098, 1019, 800 cmK1. 1H NMR (CDCl3): d 1.72 (1H,
br s, OH), 2.42–2.48 (2H, m, CH2]CH–CH2), 3.79–3.83
(2H, m, anthryl-CH2), 4.12–4.15 (1H, m, CH–OH),
5.16–5.26 (2H, m, CH2]CH), 5.84–5.93 (1H, m,
CH2]CH), 7.42–7.56 (4H, m, aromatic), 7.97–8.02
(2H, m, aromatic), 8.28–8.36 (3H, m, aromatic). 13C
NMR (CDCl3): d 34.74, 41.93, 72.18, 118.40, 124.64,
124.89, 125.71, 126.57, 129.17, 130.53, 130.62, 131.52,
134.74. ESI-MS: for C19H18O [M], [MCH]CZ263.14,
[MKOH]CZ245.13. Anal. (C19H18O) Calcd, C: 86.99, H:
6.92; found, C: 86.92, H: 6.76.
4.3.1. 1-Phenylpent-4-en-2-ol (3a).13,7k,3c Using the general
procedure (as in Section 4.3) but with 3-bromo-propene 1a
(181 mg, 1.5 mmol) and styrene epoxide 2a (60 mg,
0.5 mmol) afforded the title compound 3a (59 mg, 73%)
as a light yellow oily liquid.
4.3.2. 2-Phenylhex-5-en-3-ol (3b).3c Using the general
procedure (as in Section 4.3) but with 3-bromo-propene 1a
(181 mg, 1.5 mmol) and a-methylstyrene epoxide 2b
(67 mg, 0.5 mmol) afforded the title compound 3b (70 mg,
80%) as a light yellow oily liquid.
4.3.9. 4-Methyl-1-phenylpent-4-en-2-ol (3i).5a,16 Using
the general procedure (as in Section 4.3) but with
3-bromo-2-methyl-propene 1e (203 mg, 1.5 mmol) and
styrene epoxide 2a (60 mg, 0.5 mmol) afforded the title
compound 3i (31 mg, 35%) as a light yellow oily liquid.
4.3.3. 3-Methyl-1-phenylpent-4-en-2-ol (3c).14 Using the
general procedure (as in Section 4.3) but with 1-bromo-but-
2-ene 1b (202 mg, 1.5 mmol) and styrene epoxide 2a
(60 mg, 0.5 mmol) afforded the title compound 3c (63 mg,
71%) as a light yellow oily liquid.
4.4. Propargylation of epoxide
Pd(OAc)2 (3 mg, 0.01 mmol) was added to a solution of
propargyl bromide (1.5 mmol) in a DMSO–H2O solvent
mixture (3 ml–70 ml) and was allowed to stir for 5 min at rt.
Anhydrous SnCl2 (190 mg, 1 mmol) was added and the
reaction stirred for 6 h. Finally epoxide (0.5 mmol) was
added and the reaction was monitored by TLC. After
completion, the reaction was quenched by adding water and
ammonium fluoride. The mixture was extracted into
ethylacetate. The combined organic layer was washed
with water (4!50 ml), brine and dried over anhydrous
MgSO4. Solvent removal under reduced pressure followed
by column chromatography over silica gel 60–120 (eluent,
2% EtOAc in hexane) afforded the desired propargylated
product.
4.3.4. 4-Methyl-2-phenylhex-5-en-3-ol (3d).14b,15 Using
the general procedure (as in Section 4.3) but with 1-bromo-
but-2-ene 1b (202 mg, 1.5 mmol) and a-methylstyrene
epoxide 2b (67 mg, 0.5 mmol) afforded the title compound
3d (78 mg, 82%) as a light yellow oily liquid.
4.3.5. 1-Phenyl-3-propylpent-4-en-2-ol (3e).5c,5e Using the
general procedure (as in Section 4.3) but with 1-bromo-hex-
2-ene 1c (245 mg, 1.5 mmol) and styrene epoxide 2a
(60 mg, 0.5 mmol) afforded the title compound 3c (68 mg,
67%) as a light yellow oily liquid.
4.3.6. 2-Phenyl-4-propylhex-5-en-3-ol (3f). Using the
general procedure (as in Section 4.3) but with 1-bromo-
hex-2-ene 1c (245 mg, 1.5 mmol) and a-methylstyrene
epoxide 2b (67 mg, 0.5 mmol) gave the title compound 3f
(76 mg, 70%) as a yellow viscous liquid, syn:anti 70:30;
IR (neat) 3450, 3020, 2958, 2928, 2871, 1495, 1454,
4.4.1. 1-Phenyl-pent-4-yn-2-ol (5a).16 Using the general
procedure (as in Section 4.4) but with 3-bromo-propyne 4a
(179 mg, 1.5 mmol), and styrene epoxide 2a (60 mg,
0.5 mmol) afforded the title compound 5a (49 mg, 61%)
as a light yellow oily liquid.
1
1261, 1070, 1031, 914,743,700 cmK1. H NMR (CDCl3):
d 0.75–0.95 (3H, m, CH2CH2CH3), 1.15–1.47 (7H, m,
CH2CH2CH3CPhCHMe), 1.75 (1H, br s, OH), 1.96–2.06
(1H, m, CH2]CH–CH), 2.81–2.88 (1H, m, Ph-CH),
3.58–3.71 (1H, m, CH–OH), 4.92–5.21 (2H, m,
CH2]CH), 5.61–5.71 (1H, m, CH2]CH), 7.16–7.34 (5H,
m, Ph). 13C NMR (CDCl3): d [13.94, 14.01] (antiCsyn),
17.19, [20.16, 20.32] (antiCsyn), [33.6, 34.33] (antiCsyn),
43.24, 47.31, 77.84, 117.63, 126.19, 127.72, [128.37,
128.45] (antiCsyn), 138.05, 145.02. ESI-MS: for
C15H22O [M], [MKOH]CZ201.16. Anal. (C15H22O)
Calcd, C: 82.52, H: 10.16; found, C: 82.58, H: 10.19.
4.4.2. 2-Phenyl-hex-5-yn-3-ol (5b).6 Using the general
procedure (as in Section 4.4) but with 3-bromo-propyne 4a
(179 mg, 1.5 mmol) and a-methylstyrene epoxide 2b
(67 mg, 0.5 mmol) afforded the title compound 5b (38 mg,
43%) as a light yellow oily liquid.
4.4.3. 1-Anthryl-pent-4-yn-2-ol (5c). Using the general
procedure (as in Section 4.4) but with 3-bromo-propyne 4a
(179 mg, 1.5 mmol) and 1-(9-anthryl)-ethylene oxide 2c
(110 mg, 0.5 mmol) gave the title compound 5c (120 mg,
92%) as a yellow solid, mp 84–87 8C (dec); IR (KBr) 3442,
3295, 2925, 1670, 1653, 1600, 1457, 1317, 1261, 1074,
4.3.7. 3,3-Dimethyl-1-phenylpent-4-en-2-ol (3g).16 Using
the general procedure (as in Section 4.3) but with 1-bromo-
3-methyl-but-2-ene 1d (224 mg, 1.5 mmol), and styrene
epoxide 2a (60 mg, 0.5 mmol) afforded the title compound
3g (71 mg, 75%) as a light yellow oily liquid.
1025, 734, 700, 668 cmK1 1H NMR (CDCl3): d 1.85
.
(1H, br s, OH), 2.21–2.23 (1H, t, JZ2.6 Hz, acetylenic),
2.54–2.58 (2H, m), 3.91–3.99 (2H, m), 4.28–4.31 (1H, m),
7.44–7.59 (4H, m, aromatic), 8.00–8.05 (2H, m, aromatic),
8.34–8.41 (3H, m, aromatic). 13C NMR (50.3 MHz,
CDCl3): d 27.06, 34.16, 71.25, 71.30, 80.81, 124.47,
124.96, 125.91, 127.28, 129.23, 129.86, 130.57, 131.54.
ESI-MS: for C19H16O [M], [MCH]CZ261.12,
[MKOH]CZ243.12. Anal. (C19H16O) Calcd, C: 87.66,
H: 6.19; found, C: 87.75, H: 6.21.
4.3.8. 1-Anthrylpent-4-en-2-ol (3h). Using the general
procedure (Section 4.3) but with 3-bromo-propene 1a
(181 mg, 1.5 mmol) and 1-(9-anthryl)-ethylene oxide 2c
(110 g, 0.5 mmol) afforded the title compound 3h (109 mg,
83%) as yellow solid, mp 90–92 8C; IR (KBr) 3396, 2963,

U. K. Roy, S. Roy / Tetrahedron 62 (2006) 678–683
683
4.4.4. 3-Methyl-1-phenyl-pent-4-yn-2-ol(5d).16 Using
the general procedure (as in Section 4.4) but with
3-bromo-but-1-yne 4b (200 mg, 1.5 mmol) and styrene
epoxide 2a (60 mg, 0.5 mmol) afforded the title compound
5d (62 mg, 71%) as a light yellow oily liquid.
534–535. (e) Sinha, P.; Roy, S. Organometallics 2004, 23,
67–71. (f) Banerjee, M.; Roy, S. Org. Lett. 2004, 13, 2137–2140.
6. Banerjee, M.; Roy, U. K.; Sinha, P.; Roy, S. J. Organomet.
Chem. 2005, 690, 1422–1428.
7. Representative examples on enhancement of nucleophilic
reactivity of organostannanes by water, please see: (a)
Boldrini, G. P.; Lodi, L.; Tagliavini, E.; Tarasco, C.;
Trombini, C.; Umani-Ronchi, A. J. Org. Chem. 1987, 52,
5447–5452. (b) Kanagawa, Y.; Nishiyama, Y.; Ishii, Y.
J. Org. Chem. 1992, 57, 6988–6991. (c) Takahara, J. P.;
Masuyama, Y.; Kurusu, Y. J. Am. Chem. Soc. 1992, 114,
2577–2586. (d) Yanagiswa, A.; Inoue, H.; Morodome, M.;
Yamamoto, H. J. Am. Chem. Soc. 1993, 115, 10356–10357.
(e) Li, X.-R.; Loh, T.-P. Tetrahedron: Asymmetry 1996, 7,
1535–1538. (f) Houllemare, D.; Outurquin, F.; Paulmier, C.
J. Chem. Soc., Perkin Trans. 1 1997, 1629–1632. (g)
Okano, T.; Kiji, J.; Doi, T. Chem. Lett. 1998, 5–6. (h)
Chan, T. H.; Yang, Y.; Li, C. J. J. Org. Chem. 1999, 64,
4452–4455. (i) Ito, A.; Kishida, M.; Kurusu, Y.; Masuyama,
Y. J. Org. Chem. 2000, 65, 494–498. (j) Shibata, I.;
Yoshimura, N.; Yabu, M.; Baba, A. Eur. J. Org. Chem.
2001, 3207–3211. (k) Tan, X.-H.; Shen, B.; Deng, W.;
Zhao, H.; Liu, L.; Guo, Q.-X. Org. Lett. 2003, 5,
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4.4.5. 3,3-Dimethyl-1-phenyl-pent-4-yn-2-ol (5e).5b,6
Using the general procedure (as in Section 4.4) but with
3-bromo-3-methyl-but-1-yne 4c (220 mg, 1.5 mmol) and
styrene epoxide 2a (60 mg, 0.5 mmol) afforded the title
compound 5e (45 mg, 48%) as a light yellow oily liquid.
Acknowledgements
We thank CSIR for financial support. Research fellowship
to U.K.R. (UGC-SRF) is acknowledged.
Supplementary data
Supplementary data associated with this article can be
found, in the online version at doi: 10.1016/j.tet.2005.10.005
8. Huang, T.; Meng, Y.; Venkatraman, S.; Wang, D.; Li, C. J.
J. Am. Chem. Soc. 2001, 123, 7451–7452.
9. Thoonen, S.; Deelman, B.-J.; Koten, G. v. Tetrahedron 2003,
59, 10261–10268.
10. For interaction between polar coordinating solvent and Sn(IV)
species please see: Satchell, D. P. N.; Satchell, R. S. Chem.
Rev. 1969, 69, 251–278 and references therein.
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