Highly regio- and stereoselective iodohydroxylation of 1,2-allenylic sulfoxides in the presence of benzyl thiol

Article abstract of DOI:10.1002/adsc.201000973

The iodohydroxylation of 1,2-allenyl sulfoxides with iodine in the presence of benzyl thiol afforded 3-hydroxy-2-iodo-2(E)-alkenyl sulfides in good yields and high regio- and stereoselectivities. In this reaction it was observed that the sulfoxide functionality was reduced to sulfide and the water in the reaction mixture plays an important role for the stereoselectivity observed. A mechanism involving the attack of benzyl thiol at the positively charged sulfur atom in the five-membered intermediate 2 has been proposed. Copyright

Full text of DOI:10.1002/adsc.201000973

FULL PAPERS
DOI: 10.1002/adsc.201000973
Highly Regio- and Stereoselective Iodohydroxylation of
1,2-Allenylic Sulfoxides in the Presence of Benzyl Thiol
Minyan Wang,a Chunling Fu,a,* and Shengming Maa,*
a
Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027,
Peopleꢀs Republic of China
Fax : (+86)-21-6260-9305; e-mail: fucl@zju.edu.cn or masm@sioc.ac.cn
Received: December 27, 2010; Revised: April 22, 2011; Published online: June 30, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adcs.201000973.
Abstract: The iodohydroxylation of 1,2-allenyl sulf- reoselectivity observed. A mechanism involving the
oxides with iodine in the presence of benzyl thiol af- attack of benzyl thiol at the positively charged sulfur
forded 3-hydroxy-2-iodo-2(E)-alkenyl sulfides in atom in the five-membered intermediate 2 has been
good yields and high regio- and stereoselectivities. In proposed.
this reaction it was observed that the sulfoxide func-
tionality was reduced to sulfide and the water in the Keywords: allenes; iodohydroxylation; reduction;
reaction mixture plays an important role for the ste- sulfoxides
Introduction
ing 3-phenylthio-2-iodo-2(E)-alkenols 3.[5] In this
paper, we wish to disclose our recent studies on the
During the last 10–15 years, the reactions of allenes details of this reaction including the scope, the factors
have been shown to be very powerful in organic syn- controlling the stereoselectivity, and the mechanism.
thesis,[1] especially much attention has been paid to
the transition metal-catalyzed or -mediated transfor-
mation of allenes.[2] In addition, much interest has Results and Discussion
been shown to the regio- and stereoselective electro-
philic addition of allenes.[3–5] In one such study, we ob- According to our previous results,[5] MeCN was used
served that the halohydroxylation of 1,2-allenyl sulf- as the solvent for this type of reaction. When the re-
oxides afforded 3-phenylsulfinyl-2-halo-2(E)-alkenols action of 1,2-propadienyl phenyl sulfoxide 1a was con-
via the participation of the sulfinyl group forming a 5- ducted with 1.5 equivalents of I2 in the commercial
membered intermediate 2 (Scheme 1), which accounts MeCN in the presence of 1 equivalent of BnSH at
for the E-selectivity.[4] In a preliminary communica- 58C, a 53% yield of thioether E-3a was obtained with
tion, we have also reported the iodohydroxylation of an E/Z ratio of 96/4 [Eq. (1)]. The stereochemistry
1,2-allenyl sulfoxides in the presence of BnSH afford- was determined by the NOE study of E-3a.
Scheme 1.
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Table 1. The reaction of octa-1,2-dienyl phenyl sulfoxide 1f with I2 in the presence of BnSH.[a]
Entry
Conditions
Solvent
T [oC]
Time t [min]
Yield of 3f [%][b]
E/Z of 3f[b]
Yield of E-4f [%][b]
1
2
3
A
B
B
B
B
B
B
B
B
B
B
B
B
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
CH2Cl2
toluene
acetone
CH3NO2
dioxane
DMF
5
5
60
10
30
42
42
60
60
60
30
30
42
90
42
10
31
45
58
4
47
35
72
57
71
62
0
30/70
61/39
76/24
91/9
>99/1
96/4
–
89/11
81/19
92/8
97/3
0
3
3
À10
À20
À20
À40
À20
À20
À20
À20
r.t.
11
13
63
33
–
6
9
17
10
0
4
5c)
6
7
8
9
10
11
12
13[d]
À20
MeCN/H2O
À20
72
>99/1
16
[a]
Conditions A: a solution of 1f (0.4 mmol) in commercial MeCN (4 mL) was treated with I2 (0.6 mmol) for 5 min followed
by the addition of a solution of BnSH (0.4 mmol) in commercial MeCN (2 mL) with stirring at 58C. After the reaction
was complete, the mixture was quenched with 6 mL of water followed by the addition of a saturated aqueous solution of
Na2S2O3. Conditions B: to a flask containing a solution 1f (0.4 mmol) and BnSH (0.4 mmol) in the indicated solvent
(3 mL) was added a solution of I2 (0.6 mmol) in the indicated solvent (3 mL) with stirring. When the reaction was com-
plete as monitored by TLC, the reaction was quenched with H2O (6 mL), which was followed by the treatment with a sa-
turated aqueous solution of Na2S2O3 at 08C.
NMR yield with CH2Br2 as the internal standard.
The reaction was conducted in the absence of BnSH.
Anhydrous MeCN and 2.0 equiv. H2O were used.
[b]
[c]
[d]
However, when we tried to extend this reaction to
When anhydrous MeCN (distilled from CaH2 after
3-monosubstituted 1,2-allenyl sulfoxides, i.e., octa-1,2- refluxing over CaH2 for 5 h) was employed, the E/Z
dienyl phenyl sulfoxide 1f, the yield of 2-iodo-1-phe- ratio dropped from 91/9 to 77/23. Thus, it is obvious
nylthio-1-octen-3-ol 3f was only 10% with an E/Z that water has an impact on the stereoselectivity.
ratio of 30/70 (entry 1, Table 1). The reaction at 58C Then the effect of H2O on the stereoselectivity was
afforded 3f with 31% yield and 61/39 E/Z stereoselec- carefully studied. The reaction with 2.0 equivalents of
tivity under conditions B (entry 2, Table 1). By com- H2O afforded E-3f in 72% yield with the stereoselec-
paring entry 4 with entry 5, it should be noted that tivity being >99/1. On increasing the loading of water
BnSH is important for the formation of 3f. Without to 10.0 equivalents, the reaction did not proceed and
BnSH the major product was sulfoxide E-4f in 63% 73% of 1f was recovered.
yield (entry 5, Table 1). According to the study on the
With this set of optimized reaction conditions, we
effect of temperature on the selectivity of the reac- studied the scope of the iodohydroxylation of propa-
tion, we observed that 3f was formed in 58% yield dienyl phenyl sulfoxide 1a and the 3-monosubstituted
with 91/9 E/Z stereoselectivity when the reaction was 1,2-allenyl sulfoxide 1b–k with 1.0 equivalent of
conducted at À208C (entry 4, Table 1). Then we BnSH and 2.0 equivalents of H2O (Table 2). In all
screened the most commonly used solvents, such as these cases, the stereoselectivity was ꢀ95/5 with good
CH2Cl2, toluene, MeNO2, acetone, and 1,4-dioxane: yields.
the iodohydroxylation of 1f in these solvents afforded
However, the current reaction conditions are not
3f in moderate yields (35–72%) (entries 7–11, suitable for 3,3-disubstituted 1,2-allenyl sulfoxides
Table 1). However, DMF is poor for this type of reac- since the reaction of 1l formed a mixture of sulfides
tion. To our surprise, when 2.0 equivalents of H2O in E-3l and Z-3l with a very lower E/Z selectivity under
MeCN was used as solvent, the reaction afforded 3f the above optimized reaction conditions (entry 1,
in 72% yield together with>99/1 E/Z stereoselectiv- Table 3). Further screening led us to observe that
ity (entry 13, Table 1).
when the reaction was conducted at À408C, the E/Z
ratio was improved to 94/6 (entry 2, Table 3). Interest-
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Highly Regio- and Stereoselective Iodohydroxylation of 1,2-Allenylic Sulfoxides
Table 2. Iodohydroxylation of 3-monosubstituted 1,2-allenyl
ingly, by increasing the loading of the water to
10.0 equivalents, the stereoselectivity was improved
dramatically to >99/1 with 59% yield (entry 4,
Table 3). Decreasing the amount of I2 did not affect
the stereoselectivity (entry 5, Table 3). We also tried
the different types of quenching method, the reaction
afforded the best results when the resulting mixture
was quenched with water at À408C, then warmed up
to 08C, which was followed by treatment with a satu-
rated aqueous solution of Na2S2O3 (entry 5, Table 3).
Thus, the reactions of polysubstituted 1,2-allenyl
sulfoxides 1m–1t were conducted at À408C to afford
the sulfides 3m–3t with a highly stereoselectivity and
good yields (Table 4).
It has been reported that thiols or thiophenols may
reduce the sulfoxides to sulfides upon heating.[6] Thus,
in order to see the possibility for the formation of sul-
fide E-3a from the in situ reduction of E-4a with
BnSH, the normal iodohydroxylation product E-4a
was treated with I2 in MeCN or only BnSH in MeCN
at 58C, no reaction was observed. Then E-4a was
treated with I2 in the presence of BnSH in MeCN, the
reduction did occur with 18% yield of E-3a
(Scheme 2). Based on this, it is concluded that al-
though it is possible that the sulfide E-3 may be
formed partially via the reduction of the normal iodo-
hydroxylation product E-4 with BnSH and I2, there
must exist a major alternative pathway for the forma-
tion of the sulfide E-3.
sulfoxides in the presence of BnSH.[a]
Entry
R
Time t
[min]
Yield of
E/Z
G
E-3 [%][c]
of 3[d]
1[e]
2
3
4
5
6
7
8
9
H (1a)
CH3 (1b)
C2H5 (1c)
120
34
44
33
31
44
49
91
61
52
45
47 (E-3a)
70 (E-3b)
77 (E-3c)
75 (E-3d)
67 (E-3e)
72 (E-3f)
81 (E-3g)
65 (E-3h)
71 (E-3i)
77 (E-3j)
74 (E-3k)
>99/1
96/4
97/3
97/3
99/1
> 99/1
99/1
> 99/1
95/5
96/4
>99/1
i-C3H7 (1d)
n-C4H9 (1e)
n-C5H11 (1f)
n-C6H13 (1g)
n-C7H15 (1h)
n-C8H17 (1i)
n-C9H19 (1j)
Ph (1k)
10
11
[a]
Conditions B: to a solution of 1 (0.4 mmol), BnSH
(0.4 mmol), and H2O (0.8 mmol, 14.4 mL) in anhydrous
MeCN (3 mL) was added a solution of I2 (0.6 mmol) in
anhydrous MeCN (3 mL) with stirring at À208C. The re-
action was quenched with H2O (6 mL) at À208C, which
was followed by the treatment with a saturated aqueous
solution Na2S2O3 at 08C.
[b]
Anhydrous MeCN (distilled from CaH2 after refluxing
over CaH2 for 5 h) was used.
[c]
[d]
Isolated yield.
Thus, the reaction of 1a in the presence of BnSSBn
and I2 was also conducted with E-3a whereby E-4a
was isolated in 13% and 57% yields, respectively, in-
1
Determined by H NMR analysis using CH2Br2 as inter-
nal standard.
[e]
The reaction was conducted under conditions A and an-
hydrous MeCN was used.
Table 3. The reaction of 3,3-pentamethylenepropadienyl phenyl sulfoxide 1l with I2 in the presence of BnSH.[a]
Entry
I2 (equiv.)
T [oC]
H2O (equiv)
Time t [min]
Yield of E-3l [%][b]
E/Z of 3l[c]
Yield of E-4l [%][c]
1
2
3
4
1.5
1.5
1.5
1.5
1.2
1.2
1.2
À20
À40
À40
À40
À40
À40
À40
2.0
2.0
5.0
10.0
10.0
10.0
10.0
17
17
17
11
46
21
41
34
64
52
43/57
94/6
>99/1
>99/1
>99/1
97/3
25
34
30
59
34
5
65 (67[d])
28 (24[d])
6e)
7f)
66
42
15
0
>99/1
[a]
To a solution of 1l (0.4 mmol), BnSH (0.4 mmol) and H2O in anhydrous MeCN (4.2 mL) was added a solution of I2 in an-
hydrous MeCN (1.8 mL) with stirring. The reaction was quenched with H2O (6 mL), which was followed by the treatment
with a saturated solution of Na2S2O3 at 08C.
Anhydrous MeCN (distilled from CaH2 after refluxing over CaH2 for 5 h) was used.
NMR yield with CH2Br2 as the internal standard.
Isolated yield.
The reaction was quenched with H2O at 08C.
The reaction was quenched with a saturated aqueous solution Na2S2O3 at À408C, 42% of 1l was recovered.
[b]
[c]
[d]
[e]
[f]
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Table 4. Iodohydroxylation of poly-substituted 1,2-allenyl sulfoxides in the presence of BnSH.[a]
Entry
R1
R2
R3
Time t [min]
Yield of E-3 [%][c]
E/Z of 3[d]
1
H
H
H
H
H
H
H
n-C4H9
CH3
C2H5
C2H5
CH3
CH3
CH3
CH3
CH3
CH3 (1m)
C2H5 (1n)
Ph (1o)
i-C4H9 (1p)
C2H5 (1q)
n-C3H7 (1r)
Ph (1s)
15
20
30
20
20
21
21
19
60 (E-3m)
71 (E-3n)
64 (E-3o)
67 (E-3p)
63 (E-3q)
69 (E-3r)
62 (E-3s)
66 (E-3t)
>99/1
>99/1
>99/1
>99/1
>99/1
>99/1
>99/1
>99/1
2
3e)
4
5
6
7
8
CH3 (1t)
[a]
Conditions C: to a solution of 1 (0.4 mmol), BnSH (0.4 mmol), and H2O (4 mmol, 72 mL) in anhydrous MeCN (4.2 mL)
was added a solution of I2 (0.48 mmol) in anhydrous MeCN (1.8 mL) with stirring at À408C. After the reaction was com-
plete as monitored by TLC, the reaction was quenched with H2O (6 mL) at À408C, which was followed by the treatment
with a saturated aqueous solution of Na2S2O3 at 08C.
[b]
[c]
[d]
[e]
Anhydrous MeCN (distilled from CaH2 after refluxing over CaH2 for 5 h) was used.
Isolated yield.
1
Determined by H NMR analysis using CH2Br2 as internal standard.
1.5 equiv. I2 were added.
Scheme 2.
dicating that BnSSBn may also be partially responsi- shown in Scheme 3. The highly selective reaction of
ble for the formation of sulfide E-3a [Eq. (2)]. How- the electron-rich carbon-carbon double bond with I+
ever, no reduction of E-4a was observed with forms the iodonium intermediate. The sulfinyl oxygen
BnSSBn in the absence or presence of I2 in MeCN effects an intramolecular attack on the iodonium in-
(Scheme 2).
termediate at the 3-position affording the five-mem-
Based on these studies, we proposed a mechanistic bered charged intermediate 2,[7] which accounts for
rationale for the formation of sulfide E-3, which is the stereoselectivity of this reaction. The reaction of
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Highly Regio- and Stereoselective Iodohydroxylation of 1,2-Allenylic Sulfoxides
the positively charged intermediate 2 with BnSH
would afford intermediate E-5, which could be at- solute configuration of the product E-3g was estab-
tacked by a molecule of BnSH to afford BnSSBn. lished by the X-ray diffraction study of its oxidized
The transformation from E-5 to E-3 is the major path- product E-4g [Eq. (4) and Figure 1].[9] The result fur-
way. The minor pathway is the reaction of intermedi- ther supports our proposed mechanism shown in
ate 2 with H2O affording E-4, which may be reduced Scheme 3.
to form E-3.
Furthermore, it is quite interesting to observe that
According to the mechanism presented in E-3a would isomerize to Z-3a in the presence of I2:
Scheme 3, if an optically active 1,2-alleylic sulfoxide
with a defined axial chirality in the allene moiety
were allowed to react with I2 in the presence of
BnSH, the chirality of the allene moiety would be
transferred into the chiral center of the allylic alcohol.
In fact, it was observed that the ee value of halohy-
droxylation product E-3g is essentially equal to that
of the corresponding reactant 1g [Eq. (3)].[8] The ab-
Scheme 3.
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Table 5. The isomerization of E-2-iodo-3-phenylthio-2-
propen-1-ol.
Entry I2 (equiv.) Time t [h] Yield of 3a[b] [%] E/Z of 3a[c]
1
2
3
4
0.5
1.0
1.5
2.0
13
15
15
24
83
90
91
83
62/38
11/89
5/95
5/95
[a]
Figure 1. ORTEP representation of (R)-E-4g.
Anhydrous MeCN (distilled from CaH2 after refluxing
over CaH2 for 5 h) was used.
[b]
[c]
Isolated yield.
1
With 0.5 equivalents of I2 after 13 h at 08C, the reac-
tion of E-3a afforded an E/Z mixture of 3a (entry 1,
Table 5). When 1.5 equivalents of I2 were applied, the
reaction afforded 3a in 91% yield with a Z/E ratio of
95/5 (entry 3, Table 5). With 2.0 equivalents of I2 and
a longer reaction time, the yield dropped to 83%
(entry 4, Table 5).
Determined by H NMR analysis.
As expected, the corresponding Z isomer is much
more stable, which may be explained by the interac-
tion of the lone electron pair of the sulfur atom with
the empty orbital of I,[10] thus, a mixture of E/Z-3a in
a final ratio of 4/96 was formed after being treated
with 0.5 equivalents of I2 for 12 h [Eq. (5)], which is
in consistent with the results shown in entries 3 and 4
in Table 5.
Scheme 4.
Conclusions
We have described the highly stereoselective iodohy-
droxylation of 1,2-allenylic sulfoxides in the presence
3-Phenylthio-2-iodo-2(E)-alkenols are very useful of BnSH affording 3-hydroxy-2-iodo-2(E)-alkenyl sul-
building blocks in organic synthesis due to the exis- fides in detail. The C=C bond configuration in the
À
À
tence of the C I bond, the C S bond and the OH products is opposite to what was synthesized via the
function. The Sonogashira coupling of E-3f with a ter- iodohydroxylation of 1,2-allenyl sulfides.[4] The stereo-
minal alkyne was carried out in Et3N and DMSO selectivity depends on the amount of H2O in MeCN.
under the catalysis of PdACTHNUTRGNEUNG(PPh3)2Cl2 and CuI to afford Based on careful control experiments and a mechanis-
6 in 90% yield; the Suzuki coupling of E-3f with phe- tic study, a rationale has been proposed. It is also ob-
nylboronic acid using Na2CO3 as the base in DME served that 3-phenylthio-2-iodo-2(E)-alkenols are
and H2O (1:1) afforded 7 in 60% yield; when E-3f more stable and may be converted to 3-phenylthio-2-
was added to m-CPBA in CH2Cl2 at 08C, the sulfox- iodo-2(Z)-alkenols in the presence of I2 in MeCN.
ide product E-4f was formed in 85% yield after 2 h Further studies in this area are being conducted in
(Scheme 4).
our laboratory.
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Highly Regio- and Stereoselective Iodohydroxylation of 1,2-Allenylic Sulfoxides
MS: m/z=243.0832, calcd. for C13H16OSNa (M+ +Na):
243.0814.
Experimental Section
Anhydrous MeCN was distilled from CaH2 after refluxing
over CaH2 for 5 h.
Iodohydroxylation of 1,2-Allenylic Sulfoxides in the
Prescence of BnSH
Synthesis of the Starting Materials
Compounds 1a–h, 1k–q, 1s and 1t were prepared according
to the known procedures.[7a] Compounds 1i, 1j, and 1r were
prepared as follows.
(E)-2-Iodo-3-phenylthio-2-propen-1-ol (E-3a): A solution of
1a (82.3 mg, 0.5 mmol) in commercial MeCN (4 mL) was
treated with I2 (195.1 mg, 0.77 mmol) for 5 min followed by
the addition of a solution of BnSH (63.1 mg, 0.5 mmol) in
commercial MeCN (2 mL) with stirring. After being stirred
at 58C for 2 h, the mixture was quenched with 6 mL of
water followed by the addition of a saturated aqueous solu-
tion of Na2S2O3. The mixture was extracted with dichloro-
methane (25 mLꢂ3) and dried over anhydrous MgSO4. Fil-
tration, evaporation, and column chromatography on silica
gel (petroleum ether/ethyl acetate=10/1 ~2/1 afforded E-3a
(yield: 74.0 mg, 51%) and Z-3a[10a] (yield: 3.3 mg, 2%).
1,2-Undecadienyl Phenyl Sulfoxide (1i); Typical
Procedure[7a]
To a dried three-neck round-bottom flask were added
undec-1-yn-3-ol (1.69 g, 10 mmol), triethylamine (1.70 mL,
d=0.72 g/mL, 12 mmol, 1.22 g), and CH2Cl2 (20 mL) se-
quentially. After the mixture had beens cooled to À708C, a
solution of sulfenyl chloride (1.74 g, 12 mmol) was added
dropwise in 5 min. After being stirred at À708C for 10 min,
methyl iodide (0.1 mL, d=2.28 g/mL, 1.6 mmol, 0.23 g) was
added and the mixture was allowed to warm up naturally to
room temperature followed by quenching with water
(10 mL). The organic layer was separated, and the aqueous
layer was extracted with CH2Cl2 (10 mL). The combined or-
ganic extracts were dried over anhydrous Na2SO4. Filtration,
evaporation and chromatography on silica gel (eluent: pe-
troleum ether/ethyl acetate=8/1) of the crude product af-
1
E-3a: Oil; H NMR (300 MHz, CDCl3): d=7.38–7.18 (m,
5H, ArH), 6.94 (s, 1H, =CH), 4.37 (d, J=3.6 Hz, 2H, CH2),
2.33 (bs, 1H, OH); 13C NMR (75 MHz, CDCl3): d=134.2,
132.5, 129.7, 129.2, 127.4, 99.2, 65.6; IR (neat) n=3383,
1666, 1580, 1528, 1478, 1439 cmÀ1; MS (70 eV, EI): m/z
(%)=292 (M+, 92.72), 111 (100); anal. calcd. for C9H9SOI:
C 37.00, H 3.11; found: C 37.24, H 3.17.
1
Z-3a: Oil; H NMR (300 MHz, CDCl3): d=7.48–7.40 (m,
2H, ArH), 7.40–7.24 (m, 3H, ArH), 7.07 (t, J=0.9 Hz, 1H,
=CH), 4.30 (s, 2H, CH2), 2.00 (bs, 1H, OH).
1
forded 1i as an oil; yield: 1.68 g (61%). H NMR (300 MHz,
CDCl3): d=7.67–7.60 (m, 2H, ArH), 7.60–7.44 (m, 3H,
ArH), 6.06–6.00 (m, 1H, =CH), 5.80–5.65 (m, 1H, =CH),
2.20–2.04 (m, 2H, CH2), 1.52–1.18 (m, 12H, 6 ꢂ CH2), 0.88
(t, J=6.6 Hz, 3H, CH3); IR (neat): n=2926, 2854, 1947,
1464, 1443, 1084, 1049 cmÀ1; MS (70 eV, EI): m/z (%)=276
(M+, 11.69), 163 (100); HR-MS: m/z=276.1555, calcd. for
C17H24OS (M+): 276.1548.
E-2-Iodo-1-phenylthio-1-buten-3-ol (E-3b): To a solution
of 1b (70.6 mg, 0.4 mmol), BnSH (50.8 mg, 0.4 mmol), and
H2O (14.5 mL, 0.8 mmol) in anhydrous MeCN (3 mL) was
added a solution of I2 (3.0 mL, 0.2M in anhydrous MeCN,
0.6 mmol) within 4 min at À208C with stirring. After being
stirred at À208C for 30 min, the mixture was quenched sub-
sequently with 6 mL of water at À208C and a saturated
aqueous solution of Na2S2O3 at 08C. The mixture was ex-
tracted with dichloromethane (20 mLꢂ3), washed with
brine, and dried over anhydrous Na2SO4. Filtration, evapora-
tion, and column chromatography on silica gel (petroleum
ether/ethyl acetate=20/1–2/1) afforded E-3b (yield: 84.7 mg,
70%), Z-3b[10b] (yield: 3.4 mg, 3%), and E-4b[7a] (yield:
16.8 mg, 13%).
1,2-Dodecadienyl phenyl sulfoxide (1j): The reaction of
dodeca-1-yn-3-ol (1.41 g, 7.7 mmol), triethylamine (1.10 mL,
d=0.72 g/mL, 7.8 mmol, 0.79 g), sulfenyl chloride (0.92 g,
7.7 mmol), and methyl iodide (0.4 mL, d=2.28 g/mL,
6.4 mmol, 0.91 g) in CH2Cl2 (20 mL) at À658C afforded 1j
as an oil (eluent: petroleum ether/ethyl acetate=4/1); yield:
1
1.29 g (57%). H NMR (300 MHz, CDCl3): d=7.64–7.56 (m,
1
2H, ArH), 7.52–7.42 (m, 3H, ArH), 6.02–5.96 (m, 1H, =
CH), 5.74–5.62 (m, 1H, =CH), 2.14–2.02 (m, 2H, CH2),
1.44–1.14 (m, 14H, 7 ꢂ CH2), 0.84 (t, J=6.6 Hz, 3H, CH3);
IR (neat): n=2925, 2854, 1948, 1582, 1466, 1443, 1377, 1304,
1084, 1049 cmÀ1; MS (70 eV, EI): m/z (%)=291 (M+ +1,
1.59), 290 (M+, 0.69), 126 (100); HR-MS: m/z=291.1789,
calcd. for C18H27OS (M+ +1): 291.1777.
E-3b: Oil; H NMR (300 MHz, CDCl3): d=7.30–7.16 (m,
5H, ArH), 6.78 (d, J=0.6 Hz, 1H, =CH), 4.26–4.16 (m, 1H,
CH), 2.06 (bs, 1H, OH), 1.18 (d, J=6.3 Hz, 3H, CH3);
13C NMR (100 MHz, CDCl3): d=134.3, 130.0, 129.6, 129.2,
127.3, 109.0, 67.6, 22.9; IR (neat): n=3385, 2974, 1580, 1479,
1439, 1369, 1116, 1067, 1024, 1000 cmÀ1; MS (70 eV, EI): m/z
(%)=306 (M+, 13.05), 69 (100); HR-MS (EI): m/z=
305.9586, calcd. for C10H11SOI (M+): 305.9575.
3-Methylhexa-1,2-dienyl phenyl sulfoxide (1r): The reac-
tion of 3-methylhex-1-yn-3-ol (3.73 g, 33 mmol), Et3N
(4.2 mL, d=0.72 g/mL, 33 mmol, 3.02 g), sulfenyl chloride
(4.44 g, 30 mmol), and methyl iodide (0.68 mL, d=2.28 g/
mL, 10.9 mmol, 1.55 g) afforded 1r as an oil (eluent: petrole-
1
Z-3b: Oil; H NMR (300 MHz, CDCl3): d=7.42–7.34 (m,
2H, ArH), 7.32–7.20 (m, 3H, ArH), 7.02 (d, J=0.6 Hz, 1H,
=CH), 4.02–3.94 (m, 1H, CH), 1.79 (bs, 1H, OH), 1.28 (d,
J=6.3 Hz, 3H, CH3).
The following compounds were prepared according to this
procedure.
E-2-Iodo-1-phenylthio-1-penten-3-ol (E-3c): The reaction
of 1c (76.7 mg, 0.4 mmol), 49.3 mg (0.4 mmol) of BnSH,
14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in MeCN)
at À208C afforded E-3c (yield: 98.9 mg, 77%), Z-3c[10b]
(yield: 5.7 mg, 4%), and E-4c (yield: 16.7 mg, 12%).
1
um ether/ethyl acetate=4/1); yield: 3.10 g (47%). H NMR
(300 MHz, CDCl3): d=7.68–7.58 (m, 2H, ArH), 7.58–7.42
(m, 3H, ArH), 6.02–5.94 (m, 1H, =CH), 2.08–1.90 (m, 2H,
=CCH2), 1.88–1.72 (m, 3H, =CCH3), 1.54–1.36 (m, 2H,
CH2), 0.97–0.88 (m, 3H, CH3); IR
2873, 1949, 1580, 1443, 1374, 1341, 1164, 1083, 1039 cmÀ1
MS (70 eV, EI): m/z (%)=220 (M+, 3.42), 126 (100); HR-
ACHTUNGTREN(NUNG neat): n=2967, 2928,
;
Adv. Synth. Catal. 2011, 353, 1775 – 1786
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1781

Minyan Wang et al.
FULL PAPERS
1
E-3c: Oil; H NMR (300 MHz, CDCl3): d=7.34–7.16 (m,
108.4, 71.5, 37.0, 31.6, 24.5, 22.5, 14.0; IR (neat): n=3407,
3059, 2955, 2929, 2857, 1581, 1466, 1479, 1440, 1378, 1304,
1184, 1122, 1086, 1025, 1000 cmÀ1; MS (70 eV, EI): m/z
(%)=362 (M+, 27.40), 41 (100); HR-MS (EI): m/z=
362.0178, calcd. for C14H19SOI (M+): 362.0201.
5H, ArH), 6.88 (s, 1H, =CH), 3.91 (t, J=7.1 Hz, 1H, CH),
1.95 (bs, 1H, OH), 1.68–1.40 (m, 2H, CH2), 0.87 (t, J=
7.4 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=134.5,
131.7, 129.7, 129.2, 127.4, 107.9, 72.8, 30.1, 9.3; IR (neat): n=
3385, 3057, 2963, 2930, 2873, 1580, 1478, 1459, 1440, 1379,
1331, 1089, 1057, 1023 cmÀ1; MS (70 eV, EI): m/z (%)=320
(M+, 47.09), 291 (100); HR-MS (EI): m/z=342.9616, calcd.
for C11H13SOINa (M+ +Na): 342.9602.
E-2-Iodo-4-methyl-1-phenylthio-1-nonen-3-ol (E-3g): The
reaction of 1g (98.6 mg, 0.4 mmol), 49.7 mg (0.4 mmol) of
BnSH, 14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in
anhydrous MeCN) at À208C afforded E-3g (yield: 121.3 mg,
81%) and E-4g (yield: 27.1 mg, 17%).
1
Z-3c: Oil; H NMR (300 MHz, CDCl3): d=7.40–7.32 (m,
1
2H, ArH), 7.32–7.20 (m, 3H, ArH), 7.01 (d, J=0.3 Hz, 1H,
=CH), 3.58 (t, J=6.9 Hz, 1H, CH), 1.79 (bs, 1H, OH), 1.68–
1.42 (m, 2H, CH2), 0.87 (t, J=7.5 Hz, 3H, CH3).
E-2-Iodo-4-methyl-1-phenylthio-1-penten-3-ol (E-3d): The
reaction of 1d (81.5 mg, 0.4 mmol), 50.1 mg (0.4 mmol) of
BnSH, 14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in
MeCN) at À208C afforded E-3d (yield: 98.8 mg, 75%), Z-
3d[10b] (yield: 3.1 mg, 2%), and E-4d[7b] (yield: 23.9 mg,
17%).
E-3g: Oil; H NMR (300 MHz, CDCl3): d=7.40–7.20 (m,
5H, ArH), 6.92 (d, 1H, J=0.3 Hz ,=CH), 4.10–4.00 (m,
1H, CH), 2.17 (d, 1H, J=5.1 Hz, OH), 1.65–1.48 (m, 2H,
CH2), 1.48–1.15 (m, 8H, 4ꢂCH2), 0.89 (t, J=6.6 Hz, 3H,
CH3); 13C NMR (75 MHz, CDCl3): d=134.4, 131.2, 129.6,
129.2, 127.3, 108.5, 71.3, 36.9, 31.6, 29.0, 24.8, 22.5, 14.0; IR
(neat): n=3384, 2926, 2855, 1581, 1477, 1440, 1377, 1045,
1025 cmÀ1; MS (70 eV, EI): m/z (%)=376 (M+, 32.90), 291
(100); HR-MS (EI): m/z=376.0360, calcd. for C15H21SOI
(M+): 376.0358.
1
E-3d: Oil; H NMR (300 MHz, CDCl3): d=7.40–7.15 (m,
5H, ArH), 6.89 (d, J=0.6 Hz, 1H, =CH), 3.52 (d, J=9.0 Hz,
1H, CH), 1.96 (bs, 1H, OH), 1.78–1.65 (m, 1H, CH), 1.06
(d, J=6.9 Hz, 3H, CH3), 0.80 (d, J=6.6 Hz, 3H, CH3);
13C NMR (100 MHz, CDCl3): d=134.5, 132.3, 129.7, 129.2,
127.4, 107.2, 77.9, 34.6, 18.34, 18.32; IR (neat): n=3380,
1650, 1381, 1042, 1022 cmÀ1; MS (70 eV, EI): m/z (%)=334
(M+, 18.91), 291 (100); anal. calcd. for C12H15SOI: C 43.12,
H 4.52; found: C 43.24, H 4.86.
E-2-Iodo-1-phenylthio-1-decen-3-ol (E-3h): The reaction
of 1h (104.6 mg, 0.4 mmol), 50.3 mg (0.4 mmol) of BnSH,
14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in MeCN)
at À208C afforded E-3h[10b] (yield: 101.8 mg, 65%) and E-
4h[7a] (yield: 16.2 mg, 10%).
1
E-3h: Oil; H NMR (300 MHz, CDCl3): d=7.38–7.22 (m,
5H, ArH), 6.92 (s, 1H, =CH), 4.10–4.01 (m, 1H, CH), 2.15
(d, J=5.7 Hz, 1H, OH), 1.68–1.45 (m, 2H, CH2), 1.42–1.20
(m, 10H, 5 ꢂ CH2), 0.88 (t, J=6.8 Hz, 3H, CH3); 13C NMR
(75 MHz, CDCl3): d=134.5, 131.3, 129.7, 129.2, 127.4, 108.4,
71.4, 37.0, 31.7, 29.4, 29.2, 24.8, 22.6, 14.1; IR (neat): n=
1
Z-3d: Oil; H NMR (300 MHz, CDCl3): d=7.42–7.35 (m,
2H, ArH), 7.36–7.20 (m, 3H, ArH), 6.98 (d, J=0.9 Hz, 1H,
=CH), 3.24–3.17 (m, 1H, CH), 1.84–1.78 (m, 1H, CH), 1.78–
70 (m, 1H, OH), 0.99 (d, J=6.9 Hz, 3H, CH3), 0.78 (d, J=
6.6 Hz, 3H, CH3).
3386, 3058, 2925, 2855, 1581, 1479, 1465, 1440, 1377 cmÀ1
;
MS (70 eV, EI): m/z (%)=390 (M+, 34.45), 373 (100); anal.
calcd. for C16H23SOI: C 49.23, H 5.94; found: C 49.27, H
5.99.
E-2-Iodo-1-phenylthio-1-hepten-3-ol (E-3e): The reaction
of 1e (88.8 mg, 0.4 mmol), 50.5 mg (0.4 mmol) of BnSH,
14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in MeCN)
at À208C afforded E-3e (yield: 93.7 mg, 67%), Z-3e[10b]
(yield: 2.0 mg, 1%), and E-4e[7a] (yield: 15.9 mg, 11%).
E-2-Iodo-1-phenylthio-1-undecen-3-ol (E-3i): The reaction
of 1i (109.6 mg, 0.4 mmol), 50.4 mg (0.4 mmol) of BnSH,
14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in MeCN)
at À208C afforded E-3i (yield: 114.6 mg, 71%), Z-3i (yield:
2.1 mg, 1%), and E-4i[7a] (yield: 9.4 mg, 6%).
1
E-3e: Oil; H NMR (300 MHz, CDCl3): d=7.32–7.14 (m,
5H, ArH), 6.84 (s, 1H, =CH), 3.98 (bs, 1H, CH), 2.07 (m,
1H, OH), 1.62–1.38 (m, 2H, CH2), 1.38–1.12 (m, 4H, 2 ꢂ
CH2), 0.85 (t, J=6.9 Hz, 3H, CH3); 13C NMR (100 MHz,
CDCl3): d=134.5, 131.3, 129.7, 129.2, 127.4, 108.4, 71.4, 36.6,
1
E-3i: Oil; H NMR (300 MHz, CDCl3): d=7.38–7.20 (m,
5H, ArH), 6.92 (d, J=0.6 Hz, 1H, =CH), 4.12–4.00 (m, 1H,
CH), 2.11 (d, J=4.5 Hz, 1H, OH), 1.66–1.42 (m, 2H, CH2),
1.40–1.08 (m, 12H, 6 ꢂ CH2), 0.88 (t, J=6.9 Hz, 3H, CH3);
13C NMR (75 MHz, CDCl3): d=134.5, 131.2, 129.6, 129.2,
127.3, 108.5, 71.4, 36.9, 31.8, 29.42, 29.37, 29.2, 24.8, 22.6,
14.1; IR (neat): n=3387, 2925, 2854, 1581, 1478, 1440, 1377,
1025 cmÀ1; MS (70 eV, EI): m/z (%)=404 (M+, 24.82), 291
(100); HR-MS (EI): m/z=404.0688, calcd. for C17H25SOI
(M+): 404.0671.
26.9, 22.5, 14.0; IR (neat): n=3406, 1581, 1479, 1025 cmÀ1
;
MS (70 eV, EI): m/z (%)=348 (M+, 26.22), 331 (100); anal.
cacld. for C13H17SOI: C 44.84, H 4.92; found: C 44.93, H
4.90.
1
Z-3e: Oil; H NMR (300 MHz, CDCl3): d=7.48–7.40 (m,
2H, ArH), 7.40–7.24 (m, 3H, ArH), 7.06 (s, 1H, =CH),
3.78–3.66 (m, 1H, CH), 1.83 (d, J=5.4 Hz, 1H, OH), 1.66–
1.52 (m, 2H, CH2), 1.40–1.12 (m, 4H, 2 ꢂ CH2), 0.91 (t, J=
6.9 Hz, 3H, CH3).
1
Z-3i: Oil; H NMR (300 MHz, CDCl3): d=7.48–7.40 (m,
2H, ArH), 7.40–7.30 (m, 3H, ArH), 7.06 (s, 1H, =CH),
3.78–3.66 (m, 1H, CH), 1.81 (d, J=5.1 Hz, 1H, OH), 1.68–
1.46 (m, 2H, CH2), 1.40–1.16 (m, 12H, 6 ꢂ CH2), 0.89 (t,
J=3.3 Hz, 3H, CH3).
E-2-Iodo-1-phenylthio-1-octen-3-ol (E-3f): The reaction
of 1f (94.2 mg, 0.4 mmol), 50.7 mg (0.4 mmol) of BnSH,
14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in MeCN)
at À208C afforded E-3f (yield: 104.9 mg, 72%) and E-4f[7a]
(yield: 19.0 mg, 12%).
E-2-Iodo-1-phenylthio-1-dodecen-3-ol (E-3j): The reac-
tion of 1j (115.5 mg, 0.4 mmol), 49.3 mg (0.4 mmol) of
BnSH, 14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in
MeCN) at À208C afforded E-3j (yield: 127.5 mg, 77%), Z-
3j (yield: 4.8 mg, 3%), and E-4j (yield: 27.1 mg, 16%).
1
E-3f: Oil; H NMR (300 MHz, CDCl3): d=7.37–7.18 (m,
5H, ArH), 6.88 (s, 1H, =CH), 4.01 (t, J=6.8 Hz, 1H, CH),
1.95 (bs, 1H, OH), 1.62–1.40 (m, 2H, CH2), 1.40–1.20 (m,
6H, 3 ꢂ CH2), 0.85 (t, J=6.3 Hz, 3H, CH3); 13C NMR
(100 MHz, CDCl3): d=134.5, 131.4, 129.7, 129.3, 127.4,
1
E-3j: Oil; H NMR (300 MHz, CDCl3): d=7.30–7.14 (m,
5H, ArH), 6.84 (s, 1H, =CH), 3.98 (t, J=6.6 Hz, 1H, CH),
1782
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ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1775 – 1786

Highly Regio- and Stereoselective Iodohydroxylation of 1,2-Allenylic Sulfoxides
2.05 (bs, 1H, OH), 1.60–1.36 (m, 2H, CH2), 1.34–1.12 (m,
14H, 7 ꢂ CH2), 0.80 (t, J=6.6 Hz, 3H, CH3); 13C NMR
(100 MHz, CDCl3): d=134.5, 131.3, 129.6, 129.2, 127.4,
108.5, 71.4, 37.0, 31.8, 29.5, 29.4, 29.2, 24.8, 22.6, 14.1; IR
(neat): n=3406, 2924, 2854, 1581, 1479, 1465, 1440, 1377,
1119, 1024 cmÀ1; MS (70 eV, EI): m/z (%)=418 (M+, 13.93),
41 (100); HR-MS (EI): m/z=418.0792, calcd. for C18H27SOI
(M+): 418.0827.
(neat): n=3416, 1637, 1617, 1581, 1475, 1439 cmÀ1; MS
(70 eV, EI): m/z (%)=320 (M+, 56.43), 43 (100); anal. calcd.
for C11H13SOI: C 41.26, H 4.00; found: C 41.37, H 4.37.
E-3-Ethyl-2-iodo-1-phenylthio-1-penten-3-ol (E-3n): The
reaction of 1n (88.6 mg, 0.4 mmol), 49.6 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3n (yield: 99.9 mg, 71%) and
E-4n[7a] (yield: 15.1 mg, 10%).
1
1
Z-3j: Oil; H NMR (300 MHz, CDCl3): d=7.40–7.35 (m,
E-3n: Oil, H NMR (300 MHz, CDCl3): d=7.34–7.15 (m,
2H, ArH), 7.35–7.22 (m, 3H, ArH), 6.99 (d, J=0.6 Hz, 1H,
=CH), 3.65 (t, J=6.9 Hz, 1H, CH), 1.73 (bs, 1H, OH), 1.60–
1.40 (m, 2H, CH2), 1.36–1.08 (m, 14H, 7ꢂCH2), 0.81 (t, J=
6.9 Hz, 3H, CH3).
5H, ArH), 6.95 (s, 1H, =CH), 2.31 (bs, 1H, OH), 2.01–1.87
(m, 2H, CH2), 1.65–1.51 (m, 2H, CH2), 0.92 (t, J=7.5 Hz,
6H, 2 ꢂ CH3); 13C NMR (100 MHz, CDCl3): d=136.5,
134.3, 130.3, 129.2, 127.5, 100.3, 82.1, 33.4, 7.3; IR (neat): n=
3374, 1654, 1381, 1089, 1049 cmÀ1; MS (70 eV, EI): m/z
(%)=348 (M+, 40.04), 331 (100); HR-MS (EI): m/z=
348.0014, calcd. for C13H17SOI (M+): 348.0045.
E-2-Iodo-1-phenyl-3-phenylthio-2-propen-3-ol (E-3k): The
reaction of 1k (96.5 mg, 0.4 mmol), 50.2 mg (0.4 mmol) of
BnSH, 14.5 mL (0.8 mmol) of H2O, and I2 (3.0 mL, 0.2M in
MeCN) at À208C afforded E-3k (yield: 109.3 mg, 74%) and
E-4k (yield: 13.6 mg, 9%).
E-2-Iodo-3-phenyl-1-phenylthio-1-penten-3-ol (E-3o): The
reaction of 1o (107.8 mg, 0.4 mmol), 50.5 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (3.0 mL, 0.2M in
MeCN) at À408C afforded E-3o (yield: 101.9 mg, 64%), and
E-4o[11] (yield: 43.4 mg, 26%).
1
E-3k: Oil; H NMR (300 MHz, CDCl3): d=7.52–7.44 (m,
2H, ArH), 7.42–7.24 (m, 8H, ArH), 7.01 (s, 1H, =CH), 5.44
(d, J=5.7 Hz, 1H, CH), 2.56 (d, J=5.7 Hz, 1H, OH);
13C NMR (100 MHz, CDCl3): d=140.6, 134.2, 132.1, 129.9,
129.4, 128.5, 128.0, 127.6, 125.8, 106.4, 72.6; IR (neat): n=
3449, 3059, 3028, 2854, 1686, 1581, 1492, 1478, 1449, 1440,
1376, 1225, 1187, 1086, 1051, 1025, 1006 cmÀ1; MS (70 eV,
EI): m/z (%)=368 (M+, 5.61), 131 (100); HR-MS (EI):
m/z=367.9719, calcd. for C15H13SOI (M+): 367.9732.
1
E-3o: Oil, H NMR (300 MHz, CDCl3): d=7.61–7.52 (m,
2H, ArH), 7.43–7.20 (m, 8H, ArH), 7.06 (s, 1H, =CH), 2.69
(s, 1H, OH), 2.56–2.40 (m, 1H, one proton in CH2), 2.28–
2.13 (m, 1H, one proton in CH2), 1.05 (t, J=7.4 Hz, 3H,
CH3); 13C NMR (100 MHz, CDCl3): d=144.0, 136.1, 134.1,
130.5, 129.2, 128.3, 127.8, 127.6, 126.0, 102.5, 81.7, 33.8, 8.0;
IR (neat): n=3378, 1650, 1381, 1089, 1049 cmÀ1; MS (70 eV,
EI): m/z (%)=396 (M+, 26.33), 367 (100); HR-MS (EI):
m/z=396.0064, Calcd. for C17H17SOI (M+): 396.0045.
E-2-Iodo-3,5-dimethyl-1-phenylthio-1-hexen-3-ol (E-3p):
The reaction of 1p (92.6 mg, 0.4 mmol), 50.7 mg (0.4 mmol)
of BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3p (yield: 96.4 mg, 67%) and
E-4p[11] (yield: 42.5 mg, 28%).
E-(1-Iodo-2-phenylthio)ethenyl cyclohexanol (E-3l)
To a solution of 1l (92.1 mg, 0.4 mmol), BnSH (50.4 mg,
0.4 mmol), and H2O (72 mL, 4 mmol) in anhydrous MeCN
(4.2 mL) was added a solution of I2 (1.8 mL, 0.267M in an-
hydrous MeCN, 0.48 mmol) in 1 min at À408C with stirring.
After being stirred at À408C for 45 min, the mixture was
quenched sequentially with 6 mL of water at À408C and a
saturated aqueous solution of Na2S2O3 at 08C. The mixture
was extracted with dichloromethane (20 mL ꢂ 3), washed
with brine, and dried over anhydrous Na2SO4. Filtration,
evaporation, and column chromatography on silica gel (pe-
troleum ether/ethyl acetate=40/1~3/1) afforded E-3l (yield:
95.3 mg, 67%) and E-4l[7a] (yield: 35.6 mg, 24%).
1
E-3p: Oil, H NMR (300 MHz, CDCl3): d=7.43–7.24 (m,
5H, ArH), 6.91 (s, 1H, =CH), 2.25 (s, 1H, OH), 2.02–1.84
(m, 2H, CH2), 1.63–1.51 (m, 4H, CH3 and CH), 1.10–0.98
(m, 6H, 2 ꢂ CH3); 13C NMR (100 MHz, CDCl3): d=136.5,
132.4, 130.4, 129.2, 127.5, 102.9, 79.7, 49.4, 29.9, 29.7, 24.7,
24.41, 24.36; IR (neat): n=3257, 1634, 1578, 1445, 1369,
1011 cmÀ1; MS (70 eV, EI): m/z (%)=362 (M+, 6.96), 43
(100); HR-MS (EI): m/z=362.0184, calcd. for C14H19SOI
(M+): 362.0201.
E-3l: Oil, 1H NMR (300 Hz, CDCl3): d=7.43–7.21 (m,
5H, ArH), 6.92 (s, 1H, =CH), 2.13 (s, 1H, OH), 2.10–1.96
(m, 2H, CH2), 1.80–1.70 (m, 2H, CH2), 1.70–1.52 (m, 5H,
2ꢂCH2 and one proton in CH2), 1.42–1.14 (m, 1H, one
proton in CH2); 13C NMR (100 MHz, CDCl3): d=136.4,
132.0, 130.4, 129.2, 127.5, 105.0, 77.3, 36.5, 25.0, 21.8; IR
(neat): n=3396, 2955, 2930, 2856, 1581, 1479, 1440 cmÀ1; MS
(70 eV, EI): m/z (%)=360 (M+, 41.47), 110 (100); HR-MS
(EI): m/z=360.0094, calcd. for C14H17SOI (M+): 360.0045.
The following compounds were prepared according to this
procedure.
E-2-Iodo-3-methyl-1-phenylthio-1-penten-3-ol (E-3q): The
reaction of 1q (82.7 mg, 0.4 mmol), 50.3 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3q (yield: 84.1 mg, 63%) and
E-4q[11] (yield: 35.8 mg, 25%).
1
E-3q: Oil, H NMR (300 MHz, CDCl3): d=7.35–7.16 (m,
5H, ArH), 6.86 (s, 1H, =CH), 2.27 (bs, 1H, OH), 2.00–1.86
(m, 1H, one proton in CH2), 1.73–1.59 (m, 1H, one proton
in CH2), 1.49 (s, 3H, CH3), 0.92 (t, J=7.2 Hz, 3H, CH3);
13C NMR (100 MHz, CDCl3): d=136.3, 132.8, 130.4, 129.2,
127.5, 101.9, 79.2, 34.3, 28.3, 7.7; IR (neat): n=3463, 2969,
2932, 2876, 1581, 1477, 1455, 1440, 1374, 1348, 1289, 1160,
1091, 1025 cmÀ1; MS (70 eV, EI): m/z (%)=334 (M+, 6.66),
43 (100); HR-MS (EI): m/z=333.9917, calcd. for C12H15SOI
(M+): 333.9888.
E-3-Iodo-2-methyl-4-phenylthio-3-buten-2-ol (E-3m): The
reaction of 1m (77.0 mg, 0.4 mmol), 50.0 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3m (yield: 76.6 mg, 60%) and
E-4m[7a] (yield: 27.2 mg, 20%).
1
E-3m: Oil; H NMR (300 MHz, CDCl3): d=7.44–7.23 (m,
E-2-Iodo-3-methyl-1-phenylthio-1-hexen-3-ol (E-3r): The
reaction of 1r (89.0 mg, 0.4 mmol), 50.2 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
5H, ArH), 6.88 (s, 1H, =CH), 2.40 (d, J=11.4 Hz, 1H,
OH), 1.61 (s, 6H, 2ꢂCH3); 13C NMR (100 MHz, CDCl3):
d=136.1, 131.8, 130.4, 129.2, 127.6, 103.0, 76.8, 29.8; IR
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FULL PAPERS
MeCN) at À408C afforded E-3r (yield: 96.5 mg, 69%) and
E-4r[11] (yield: 41.0 mg, 28%).
E-3r: Oil, H NMR (300 MHz, CDCl3): d=7.45–7.23 (m,
in CH2Cl2 (1 mL). The mixture was stirred at 08C. After 2 h,
a saturated aqueous solution of NaHCO3 (2 mL) was added.
The organic layer was separated, and the aqueous layer was
extracted with CH2Cl2 (10 mLꢂ3). The combined organic
layer was dried over Na2SO4, Filtration, evaporation and
flash chromatography (eluent: petroleum ether/ethyl ace-
tate=4:1) afforded E-4f as a white solid; yield: 64.8 mg
(85%); mp 89.2–91.08C (Et2O/n-hexane). 1H NMR
(300 MHz, CDCl3): d=7.74–7.48 (m, 5H, ArH), [7.00 (s,
0.69H), 6.94 (s, 0.30H),=CH], [4.61 (bs, 0.50H), 3.29 (bs,
0.26H), OH], 4.55–4.38 (m, 1H, CH), 1.82–1.60 (m, 1H, one
proton in CH2), 1.60–1.18 (m, 7H, one proton in CH2 +3ꢂ
CH2), 1.02–0.82 (m, 3H, CH3); IR (KBr): n=3349, 3058,
2950, 2929, 2857, 1582, 1443, 1302, 1082, 1034 cmÀ1; MS
(70 eV, EI): m/z=378 (M+ +1, 0.32), 361 (M+ÀOH), 125
(100); anal. calcd. for C14H19SO2I: C 44.45, H 5.06; found: C
44.55, H 5.05.
1
5H, ArH), 6.91 (s, 1H, =CH), 2.37 (s, 1H, OH), 2.02–1.87
(m, 1H, one proton in CH2), 1.76–1.61 (m, 1H, one proton
in CH2), 1.57 (s, 3H, CH3), 1.52–1.38 (m, 2H, CH2), 0.97 (t,
J=7.4 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): d=
136.4, 132.6, 130.4, 129.2, 127.5, 102.2, 79.1, 43.8, 28.7, 16.8,
14.3; IR (neat): n=3453, 3058, 2959, 2930, 2870, 1581, 1476,
1439, 1373, 1324, 1159, 1025 cmÀ1; MS (70 eV, EI): m/z
(%)=348 (M+, 22.95), 43 (100); HR-MS (EI): m/z=
348.0086, calcd. for C13H17SOI (M+): 348.0045.
E-3-Iodo-2-phenyl-4-phenylthio-3-buten-2-ol (E-3s): The
reaction of 1s (101.4 mg, 0.4 mmol), 50.4 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3s (yield: 95.1 mg, 62%) and
E-4s[11] (yield: 42.8 mg, 27%).
1
E-3s: Oil, H NMR (300 MHz, CDCl3): d=7.60–7.52 (m,
The following compounds were prepared according to this
procedure.
2H, ArH), 7.42–7.20 (m, 8H, ArH), 7.04 (s, 1H, =CH), 2.94
(s, 1H, OH), 1.97 (s, 3H, CH3); 13C NMR (100 MHz,
CDCl3): d=144.8, 135.7, 133.5, 130.5, 129.2, 128.4, 127.9,
127.7, 125.7, 103.8, 79.2, 29.9; IR (neat): n=3458, 3058,
3026, 2980, 2931, 1599, 1581, 1492, 1477, 1440, 1372, 1184,
1091, 1068, 1026, 1001 cmÀ1; MS (70 eV, EI): m/z (%)=382
(M+, 39.37), 43 (100); HR-MS (EI): m/z=381.9859, calcd.
for C16H15SOI (M+): 381.9888.
E-3-Iodo-2-methyl-4-phenylthio-3-octen-2-ol (E-3t): The
reaction of 1t (99.4 mg, 0.4 mmol), 50.2 mg (0.4 mmol) of
BnSH, 72 mL (4 mmol) of H2O, and I2 (1.8 mL, 0.267M in
MeCN) at À408C afforded E-3t (yield: 99.7 mg, 66%) and
E-4t[7a] (yieled: 28.7 mg, 18%).
E-2-Iodo-4-methyl-1-phenylsulfinyl-1-nonen-3-ol (E-4g):
The reaction of E-3g (75.6 mg, 0.2 mmol) and m-CPBA
(51.9 mg, 0.3 mmol) in CH2Cl2 (2 mL) at 08C for 1 h afford-
ed E-4g as a white solid; yield: 67.4 mg (86%); mp 96.1–
96.78C (Et2O/n-hexane). 1H NMR (300 MHz, CDCl3): d=
7.74–7.59 (m, 2H, ArH), 7.59–7.46 (m, 3H, ArH), [7.00 (s,
0.63H), 6.93 (s, 0.36H),=CH], [4.87 (d, J=3.6 Hz, 0.61H),
3.81 (d, J=6.0 Hz, 0.34H), OH], 4.52–4.35 (m, 1H, CH),
1.80–1.58 (m, 1H, one proton in CH2), 1.56–1.13 (m, 9H,
one proton in CH2 + 4 ꢂ CH2), 0.96–0.80 (m, 3H, CH3);
IR (KBr): n=3358, 3060, 2953, 2926, 2855, 1582, 1443, 1082,
1033 cmÀ1; MS (70 eV, EI): m/z (%)=393 (M+ +1, 0.05),
375 (M+ÀOH), 217 (100); anal. calcd. for C15H21SO2I: C
45.92, H 5.40; found: C 46.09, H 5.39.
E-3t (Eluent: petroleum ether/ethyl ether=40/1–1/1): oil,
1H NMR (300 MHz, CDCl3): d=7.35–7.24 (m, 5H, ArH),
4.90 (s, 1H, OH), 2.48–2.40 (m, 2H, CH2), 1.67 (s, 6H, 2 ꢂ
CH3), 1.58–1.48 (m, 2H, CH2), 1.33–1.20 (m, 2H, CH2), 0.86
(t, J=7.4 Hz, 3H, CH3); 13C NMR (75 MHz, CDCl3): d=
134.4, 133.7, 130.1, 129.2, 127.3, 122.5, 76.8, 44.5, 32.8, 29.6,
AHCTUNGTREG(NNUN 3R,E)-2-Iodo-4-methyl-1-phenylsulfinyl-1-nonen-3-ol
[(R)-E-4g]: The reaction of (R)-E-1g (75.9 mg, 98.0% ee,
0.2 mmol), m-CPBA (52.2 mg, 0.3 mmol) in CH2Cl2 at 08C
for 1 h afforded (R)-E-4g as a white solid; yield: 65.8 mg
(96.9% ee, 83%); mp 123.8–124.68C (Et2O/n-hexane).
22.2, 13.9; IR (neat): n=3380, 1650, 1381, 1089, 1049 cmÀ1
;
MS (70 eV, EI): m/z (%)=376 (M+, 9.07), 43 (100); HR-MS
HPLC
(Chiralcel;
AD-H,
hexane/i-PrOH=95/5,
(EI): m/z=376.0390, calcd. for C15H21SOI (M+): 376.0358.
0.7 mLminÀ1, l=254 nm): tr =19.0 (minor), 20.7 (major),
22.7 (major), 29.5 (minor); [a]2D0: À37.1 (c 0.97, CHCl3).
1H NMR (300 MHz, CDCl3): d=7.72–7.60 (m, 2H, ArH),
7.60–7.51 (m, 3H, ArH), [6.99 (s, 0.64H), 6.95 (s, 0.36H),=
CH], 4.49–4.38 (m, 1H, CH), [3.72 (d, J=4.5 Hz, 0.63H),
2.62 (d, J=7.2 Hz, 0.35H), OH], 1.80–1.62 (m, 1H, one
proton in CH2), 1.60–1.18 (m, 9H, one proton in CH2 +4ꢂ
CH2), 0.96–0.84 (m, 3H, CH3); IR (KBr): n=3303, 3008,
2924, 2855, 1581, 1442, 1318, 1077, 1036 cmÀ1; MS (70 eV,
EI): m/z (%)=393 (M+ +1, 0.09), 375 (M+ÀOH), 217 (100);
anal. calcd. for C15H21SO2I: C 45.92, H 5.40; found: C 46.23,
H 5.42.
ACHTUNGTRENNUNG(3R,E)-2-Iodo-4-methyl-1-phenylthio-1-nonen-3-ol [(R)-
E-3g]: The reaction of R-1g (99.5 mg, 99.4% ee, 0.4 mmol),
48.8 mg (0.4 mmol) of BnSH, 14.5 mL (0.8 mmol) of H2O,
and I2 (3.0 mL, 0.2M in anhydrous MeCN) after 48 min at
À208C afforded (R)-E-3g as an oil; yield: 117.4 mg (98.5%
ee, 78%). HPLC (Chiralcel OD-H, hexane/i-PrOH=95/5,
0.8 mLminÀ1, l=254 nm): tr =10.9 (major), 19.3 (minor);
1
[a]2D0: +117.8 (c 0.82, CHCl3); H NMR (300 MHz, CDCl3):
d=7.40–7.22 (m, 5H, ArH), 6.92 (s, 1H, =CH), 4.10–4.00
(m, 1H, CH), 2.07 (d, 1H, J=5.4 Hz, OH), 1.66–1.48 (m,
2H, CH2), 1.48–1.10 (m, 8H, 4 ꢂ CH2), 0.89 (t, J=6.5 Hz,
3H, CH3); 13C NMR (75 MHz, CDCl3): d=134.5, 131.2,
129.6, 129.2, 127.3, 108.5, 71.4, 36.9, 31.7, 29.0, 24.8, 22.5,
14.1; IR (neat): n=3367, 3058, 2953, 2927, 2855, 1581, 1479,
1466, 1439, 1045, 1024 cmÀ1; MS (70 eV, EI): m/z (%)=376
(M+, 35.19), 291 (100); HR-MS (EI): m/z=376.0363, calcd.
for C15H21SOI (M+): 376.0358.
Z-7-Phenylthiomethylene-8-tridecyn-6-ol (6)
A mixture of E-3f (73.0 mg, 0.2 mmol), Et3N (0.8 mL), 1-
hexyne (33.2 mg, 0.4 mmol), PdACTHUNRGTNEG(UN PPh3)2Cl2 (7.1 mg,
0.01 mmol), CuI (7.6 mg, 0.4 mmol), and DMSO (0.8 mL)
was heated at 408C over a period of 5 h under nitrogen and
monitored by TLC. After the reaction mixture had been
cooled to room temperature, 10 mL of ethyl ether was
added. Filtration, evaporation and column chromatography
on silica gel (eluent: petroleum ether/ethyl acetate=40:1)
E-2-Iodo-1-phenylsulfinyl-1-octen-3-ol (E-4f)
A solution of m-CPBA (52.2 mg, 0.3 mmol) in CH2Cl2
(1 mL) was added to a solution of E-3f (73.3 mg, 0.2 mmol)
1784
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Adv. Synth. Catal. 2011, 353, 1775 – 1786

Highly Regio- and Stereoselective Iodohydroxylation of 1,2-Allenylic Sulfoxides
1
gave 6; yield: 57.2 mg (90%). H NMR (300 MHz, CDCl3): References
d=7.42–7.20 (m, 5H, ArH), 6.57 (s, 1H, =CH), 4.57 (t, J=
6.8 Hz, 1H, CH), 2.35 (t, J=6.9 Hz, 2H, CH2) 1.94 (bs, 1H,
OH), 1.80–1.22 (m, 12H, 6ꢂCH2), 1.00–0.84 (m, 6H, 2ꢂ
CH3); 13C NMR (75 MHz, CDCl3): d=135.0, 130.6, 129.6,
129.1, 127.13, 127.08, 93.0, 77.1, 70.0, 36.1, 31.7, 30.8, 25.0,
22.6, 22.0, 19.1, 14.0, 13.6; IR (neat): n=3440, 2956, 2931,
[1] a) Allenes in Organic Synthesis, (Eds.: H. F. Schuster;
G. M. Coppola), John Wiley & Sons, New York, 1984;
b) The Chemistry of Ketenes, Allenes, and Related Com-
pounds, Part 1, (Ed.: S. Patai), John Wiley & Sons, New
York, 1980; c) Modern Allene Chemistry, (Eds.: N.
Krause; A. S. K. Hashmi), Wiley-VCH, Weinheim,
2004; d) Cumulenes and Allenes, in: Science of Synthe-
sis, Georg. Thieme Verlag, Vol. 44, 2008; e) S. Ma,
Chem. Rev. 2005, 105, 2829; f) S. Ma, Acc. Chem. Res.
2003, 36, 701; g) L. K. Sydnes, Chem. Rev. 2003, 103,
1133.
2859, 2212, 1583, 1479, 1466, 1440, 1379, 1089, 1025 cmÀ1
;
MS (70 eV, EI): m/z (%)=316 (M+, 100); HR-MS (EI):
m/z=316.1867, calcd. for C20H28SO (M+): 316.1861.
Z-2-Phenyl-1-phenylthio-1-octen-3-ol (7)
A mixture of E-3f (73.1 mg, 0.2 mmol), 1,2-dimethoxyethane
(1 mL), Na2CO3 (64.3 mg, 0.6 mmol), H2O (1 mL), phenyl-
boronic acid (27.2 mg, 0.22 mmol), and PdACTHNURTGNENG(U OAc)2 (2.4 mg,
[2] a) S. Ma, Handbook of Organic Synthesis, (Ed.: E. Ne-
gishi), John Wiley and Sons, New York, 2002, p 1491;
b) M. A. Tius, Acc. Chem. Res. 2003, 36, 284; c) L. L.
Wie, H. Xiong, R. P. Hsung, Acc. Chem. Res. 2003, 36,
773; d) R. Zimmer, C. U. Dinesh, E. Nadanan, F. A.
Khan, Chem. Rev. 2000, 100, 3067; e) A. S. K. Hashmi,
Angew. Chem. 2000, 112, 3737; Angew. Chem. Int. Ed.
2000, 39, 3590; f) S. Ma, Pd-Catalyzed two- or three-
component cyclization of functionalized allenes, in:
Topics in Organometallic Chemisty, (Ed.: J. Tsuji)
Springer-Verlag, Heidelberg, 2005, p 187; g) L. Brands-
ma, N. A. Nedolya, Synthesis 2004, 735.
0.01 mmol) was heated at 308C under nitrogen for 12 h.
After the reaction was complete as monitored by TLC,
5 mL of ethyl ehter were added. Filtration and evaporation,
and column chromatography on silica gel (eluent: petroleum
ether/ethyl acetate=20:1) gave 7; yield: 37.6 mg (60%).
1H NMR (300 MHz, CDCl3): d=7.50–7.18 (m, 10H, ArH),
6.42 (s, 1H, =CH), 5.06–4.92 (m, 1H, CH), 2.15 (d, J=
4.2 Hz, OH), 1.82–1.68 (m, 1H, one proton in CH2), 1.68–
1.54 (m, 1H, one proton in CH2), 1.54–1.38 (m, 1H, one
proton in CH2), 1.38–1.20 (m, 5H, one proton in CH2 + 2 ꢂ
CH2), 0.86 (t, J=6.6 Hz, 3H, CH3); 13C NMR (75 MHz,
CDCl3): d=144.2, 139.5, 135.9, 129.3, 129.1, 128.1, 127.9,
127.4, 126.8, 124.5, 72.2, 35.6, 31.6, 25.5, 22.5, 14.0; IR
(neat): n=3417, 3057, 3019, 2954, 2929, 2857, 1582, 1491,
1479, 1440, 1378, 1088, 1025 cmÀ1; MS (70 eV, EI): m/z
(%)=312 (M+, 29.56), 241 (100); HR-MS (EI): m/z=
312.1550, calcd for C20H24SO (M+): 312.1548.
[3] For a recent review, see: S. Ma, Ionic Additions to Al-
lenes, in: Topics in Modern Allene Chemistry 2, (Eds.:
N. Krause; A. S. K. Hashmi), Wiley-VCH, Weinheim,
2004.
[4] For an account, see: S. Ma, Acc. Chem. Res. 2009, 42,
1679.
[5] C. Fu; X. Huang, S. Ma, Tetrahedron Lett. 2004, 45,
6063.
[6] a) T. J. Wallace, J. Am. Chem. Soc. 1964, 86, 2018;
b) T. J. Wallace, J. J. Mahon, J. Am. Chem. Soc. 1964,
86, 4099.
Typical procedure for the Isomerization of Z-2-Iodo-
3-phenylthio-2-propen-1-ol (Z-3a)
[7] a) S. Ma, H. Ren, Q. Wei, J. Am. Chem. Soc. 2003, 125,
4817. For isolation of the five-membered intermediates,
see: b) C. Zhou, C. Fu, S. Ma, Angew. Chem. 2007, 119,
4457; Angew. Chem. Int. Ed. 2007, 46, 4379; c) C.
Zhou, C. Fu, S. Ma, Tetrahedron 2007, 63, 7612. For a
similar effect of sulfoxide on such electrophilic addition
reactions, see: d) J. L. G. Ruano, V. Marcos, J. Alemꢃn,
Angew. Chem. 2009, 121, 3201; Angew. Chem. Int. Ed.
2009, 48, 3155.
To a solution of E-3a (61.8 mg, 0.21 mmol) in anhydrous
MeCN (3 mL) was added I2 (82.4 mg, 0.32 mmol) at 08C.
After 15 h with stirring, the mixture was quenched with
6 mL of water followed by the addition of a saturated aque-
ous solution of Na2S2O3. The mixture was extracted with di-
chloromethane (25 mL ꢂ 3), washed with brine, and dried
over anhydrous MgSO4. After evaporation, the ratio of E-
3a/Z-3a (5/95) was determined by NMR analysis. Column
chromatography on silica gel (petroleum ether/ethyl ace-
tate=10/1) afforded Z-3a as an oil; yield: 56.4 mg (91%).
[8] a) J. L. Garcꢄa Ruano, J. Alemꢃn, M. B. Cid, M. ꢅ.
ˇ
Fernꢃndez- Ibꢃnez, M. C. Maestro, M. R. Mart, A. M.
Martꢄn-Castro, Asymmetric Transformation Mediated
by Sulfinyl Groups, in: Organosulfur Chemistry in
Asymmetric Synthesis, (Eds.: T. Toru, C. Bolm), Wiley-
Acknowledgements
ˇ
VCH, Weinheim, pp 55–159; b) M. C. Carreno, G.
Hernꢃndez-Torres, M. Ribagorda, A. Urbano, Chem.
Commun. 2009, 41, 6129.
Financial support from the National Natural Science Founda-
tion of China (No. 20732005, 20972135) and Zhejiang Pro-
vincial Natural Science Foundation of China (No. Y4090217)
is greatly appreciated. We thank Mr. B. Wan in this group for
reproducing the preparation of E-3d in Table 3 and E-3n and
E-3t in Table 5, Shengming Ma is a Qiu Shi Adjunct Profes-
sor at Zhejiang University.
[9] Crystal data for compound E-4g: C15H21SO2I, MW=
392.28, orthorhombic, space group P 21, final R indices
[I> 2s(I)], R1=0.0325, wR2=0.0680; R indices (all
data), R1=0.0433, wR2=0.0726; a=6.4601(4) ꢆ, b=
14.3005(6) ꢆ, c=18.8441(8) ꢆ, a=90.008, b=90.008,
g=90.008, V=1740.87(14) ꢆ3, T=293(2) K, Z=4, re-
flections collected/unique 15480/3184 (Rint =0.0312),
number of observations [>2s(I)] 2678, parameters:
186. Supplementary crystallographic data have been
Adv. Synth. Catal. 2011, 353, 1775 – 1786
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1785

Minyan Wang et al.
FULL PAPERS
deposited at the Cambridge Crystallographic Data
Centre, CCDC 822024. These data can be obtained
free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[10] a) S. Ma, X. Hao, X. Huang, Org. Lett. 2003, 5, 1217;
b) S. Ma, X. Hao, X. Meng, X. Huang, J. Org. Chem.
2004, 69, 5720.
[11] C. Fu, G. Chen, Y. Deng, X. Huang, S. Ma, Chin. J.
Chem. 2004, 22, 990.
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Adv. Synth. Catal. 2011, 353, 1775 – 1786