Rh(II)-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides

Article abstract of DOI:10.1016/j.tet.2012.03.032

In this paper, Rh₂(OAc)₄-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides is reported. A series of tosylhydrazones derived from aldehydes were successfully used for [2,3]-sigmatropic rearrangement by reaction with either allylic phenyl sulfides or propargyl phenyl sulfides. The reaction conditions were optimized and afforded the products in moderate to good yields. In addition, a novel and convenient approach for the synthesis of cyclobutenones and cyclopropanes has been developed through direct oxidation of the rearrangement products.

Full text of DOI:10.1016/j.tet.2012.03.032

Tetrahedron 68 (2012) 5234e5240
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Rh(II)-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from
N-tosylhydrazones and sulfides
,
,
,
b
a,
b,
a,
*
Yuye Li a b, Zhongxing Huang a, Xinhu Wu a b, Peng-Fei Xu b , Jing Jin , Yan Zhang
*
*
, Jianbo Wang
a Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education,
College of Chemistry, Peking University, Beijing 100871, China
b State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China
a r t i c l e i n f o
a b s t r a c t
Article history:
In this paper, Rh2(OAc)4-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-to-
sylhydrazones and sulfides is reported. A series of tosylhydrazones derived from aldehydes were suc-
cessfully used for [2,3]-sigmatropic rearrangement by reaction with either allylic phenyl sulfides or
propargyl phenyl sulfides. The reaction conditions were optimized and afforded the products in mod-
erate to good yields. In addition, a novel and convenient approach for the synthesis of cyclobutenones
and cyclopropanes has been developed through direct oxidation of the rearrangement products.
Ó 2012 Elsevier Ltd. All rights reserved.
Received 3 February 2012
Received in revised form 3 March 2012
Accepted 9 March 2012
Available online 23 March 2012
Keywords:
[2,3]-Sigmatropic rearrangement
Sulfur ylides
N-Tosylhydrazone
Allylic phenyl sulfides
Propargyl phenyl sulfides
1. Introduction
accessible for the rearrangement. However, due to the problem of
stability, the electron-withdrawing substituent is generally re-
[2,3]-Sigmatropic rearrangement of sulfur ylides is one of the
most versatile bond reorganization processes in organic chemistry,
which offers a platform for the formation of CeC and CeS bonds.1
Sulfur ylides, the key intermediates in the rearrangement, can be
obtained through various transformations, of which the most tra-
ditional one is the deprotonation of sulfonium salts promoted by
base.2 Although this method has been widely utilized in the [2,3]-
sigmatropic rearrangement of sulfur ylides, it suffers from certain
disadvantages, such as the necessity of prior preparation of sulfo-
nium salts and inevitable use of stoichiometric strong base.
The transition-metal-catalyzed reaction of diazo compounds
with allylic sulfides, known as DoyleeKirmse reaction, provides an
alternative approach to generate sulfur ylides and to have sub-
sequent [2,3]-sigmatropic rearrangement.3,4 In these processes, the
electron-deficient metal carbenes derived from diazo compounds
reactreadily withsulfidestoaffordsulfurylides,whichavoidstheuse
of stoichiomeric strong base. A plethora of examples utilizing this
methodhave beenreportedinrecentliterature,5 inwhichcopperand
rhodium complexes appear to be the most efficient catalysts.
The introduction of diazo compounds has many advantages over
the traditional deprotonation and renders the sulfur ylides more
quired in the a
-position of isolable diazo compounds.4b,6 This
limitation narrows the application of diazo compounds to consid-
erable extent in this kind of catalytic rearrangement of sulfur ylides.
The fact that diazo compounds can be generated in situ from N-
tosylhydrazones through BamfordeStevenseShapiro reaction has
long been established.7 N-Tosylhydrazones have been used as the
source of unstable diazo compounds in various transition-metal-
catalyzed transformations.8e10 Metal carbene species were in-
volved as vital intermediates in these reactions. Inspired by these
facts and as a continuation of our previous work on the [2,3]-
sigmatropic rearrangement of sulfur ylides,5a,b,d,h we conceived to
introduce N-tosylhydrazones to the typical reaction system of
DoyleeKirmse reaction. Herein, we report the Rh(II)-catalyzed
[2,3]-sigmatropic rearrangement of sulfur ylides derived from N-
tosylhydrazones and sulfides (Scheme 1).
2. Results and discussion
Initially, we explored a series of catalysts for the reaction of 1a
and 2 (Table 1). Both traditional Cu(I) and Rh(II) catalysts were
observed to work for the reaction and led to rearrangement prod-
ucts. When 1.0 equiv of N-tosylhydrazone 1a and 1.0 equiv of allylic
phenyl sulfide 2 were stirred in 1,4-dioxane at 90 ꢀC, using LiOtBu as
base, catalytic Rh2(OAc)4 afforded the desired product 3a in 53%
* Corresponding authors. Tel./fax: þ86 10 6275 7248; e-mail address: wangjb@
pku.edu.cn (J. Wang).
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.03.032

Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
5235
tosylhydrazones. The yield could be improved significantly when
sulfide was used in excess. Further experiments showed that the
mixture of sulfides and N-tosylhydrazones with 2.5:1 ratio gave the
best result (entry 11). Finally, it was noted that no obvious enan-
tioselectivity was observed even the reaction was carried out by
either chiral dirhodium catalysts or copper(I) salts with chiral
ligands.
With the above results in hand, we further proceeded to ex-
amine the reaction time. It was observed that the product could be
obtained in 81% yield when the reaction was worked up after 3 h. A
little improvement could be observed with longer reaction time
when the reaction was carried out overnight (entry 14). The yields
were decreased to certain extents with shorter reaction time (en-
tries 12 and 13). A wide range of temperatures were further
screened for the reaction. The temperature of 90 ꢀC was found to be
appropriate for this reaction, while the yield became lower
whenever the temperature was increased (entries 15 and 16) or
decreased (entries 17e19).
After acquiring the optimized conditions of the reaction, we
started to explore the scope of the N-tosylhydrazones for the re-
action (Tables 2 and 3). Generally, both allyl and propargyl sulfides
underwent the rearrangement reaction smoothly and so were the
substituted N-tosylhydrazones, all affording the rearrangement
products in good to excellent yields.
Scheme 1. [2,3]-Sigmatropic rearrangement of sulfur ylides.
Table 1
Optimization of reaction conditionsa
Entry
Solvent
Base
Temp (ꢀC)
Time (h)
Yieldb (%)
Table 2
Reaction of N-tosylhydrazones 1aeq with allyl phenyl sulfide 2a
1
2
3
4
5
6
7
8
1,4-Dioxane
ClCH2CH2Cl
CH3CN
THF
Toluene
LiOtBu
LiOtBu
LiOtBu
LiOtBu
LiOtBu
NaOtBu
KOtBu
K2CO3
K3PO4
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
90
90
90
90
90
90
90
90
90
90
90
90
90
90
110
100
80
70
50
3
3
3
3
3
3
3
3
3
3
3
2
1
12
3
3
3
3
53
46
40
50
38
43
46
30
27
58
81
78
72
75
62
73
75
74
43
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
Entry
R
Product 3
Yieldb (%)
9
1
2
3
4
5
6
Ph
3a
3b
3c
3d
3e
3f
81
75
76
65
78
74
74
71
81
85
66
18
88
74
84
18
48
10
11
12
13
14
15
16
17
18
19
p-NO2C6H4
o-BrC6H4
m-BrC6H4
p-BrC6H4
p-ClC6H4
7
8
9
3,4-Cl2C6H3
p-MeO2CC6H4
p-PhC6H4
3g
3h
3i
10
11
12
13
14
15
16
17
o-CH3C6H4
m-CH3C6H4
p-CH3OC6H4
2,6-(CH3)2C6H3
3,5-(CH3O)2C6H3
2-Naphthyl
2-Furyl
3j
3k
3l
3m
3n
3o
3p
3q
3
a
From entry 1 to 10: the reaction was carried out with 1.0 equiv of N-tosylhy-
drazone 1a and 1.0 equiv of sulfides 2. From entry 11 to 19: the reaction was carried
out with 1.0 equiv of N-tosylhydrazone 1a and 2.5 equiv of sulfides 2.
b
Isolated yields after column chromatography.
(E)-PhCH]CH
yield (Table 1, entry 1), while the performance of copper catalyst
was rather poor. Rh2(OAc)4 was consequently chosen as the catalyst
for the reaction.
a
All reactions were performed with N-tosylhydrazones 1aeq (0.5 mmol,
1.0 equiv), Rh2(OAc)4 (0.005 mmol, 1 mol %), and Cs2CO3 (0.75 mmol, 1.5 equiv) in
5 mL of 1,4-dioxane, with addition of allyl phenyl sulfide 2 (1.25 mmol, 2.5 equiv),
followed by stirring 3 h at 90 ꢀC.
The reaction condition was subsequently optimized (Table 1).
Firstly, it turned out that the reaction could be carried out in various
solvents. The reaction in THF and 1,4-dioxane afforded the desired
product in similar yield (entries 1 and 4). While 1,2-dichloroethane
(DCE) gave the product in lower yield (entry 2). Both polar solvent
CH3CN and apolar solvent toluene led to lower yields (entries 3 and
5). It was observed that the effect of solvent was indistinctive when
LiOtBu was used as the base. Secondly, we explored the effect of
base. On one hand, the reactions with NaOtBu and KOtBu afforded
the product in moderate yields similar to that with LiOtBu (entries 6
and 7), while Cs2CO3 was found to be the optimal base (entry 10).
On the other hand, the reactions with K2CO3 and K3PO4 were
proved to be disfavored (entries 8 and 9). Finally, we attempted to
examine the effect of the ratio of the two substrates on the reaction.
It turned out that the yield of the reaction was not satisfactory
when allylic phenyl sulfide reacted with the same equivalent of N-
b
Isolated yields after column chromatography.
The results of reaction between N-tosylhydrazones 1aeq and
allylic phenyl sulfide 2 under optimized conditions were summa-
rized in Table 2. The electronic effects of the substituents on
a car-
bon of N-tosylhydrazones were investigated. To our delight, most
substrates bearing either electron-rich or electron-deficient sub-
stituents afforded the rearrangement products in excellent yields.
For the N-tosylhydrazones containing p-NO2C6H4, p-BrC6H4, p-
ClC6H4, 3,4-Cl2C6H3 or p-MeO2CC6H4, relatively high yield of the
rearrangement products were obtained (entries 2, 5, and 6e8). The
reaction of substrates possessing o-BrC6H4 and p-PhC6H4 also
proceeded smoothly (entries 3 and 9). However, when the sub-
stituent was m-BrC6H4, the expected product was isolated in a little
lower yield (entry 4).

5236
Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
Table 3
a novel approach for the synthesis of cyclobutenones, which con-
Reaction of N-tosylhydrazones 1 with propargyl phenyl sulfide 4a
tains three highly efficient steps.11a Although this method dem-
onstrates potential in organic synthesis, the starting materials, such
as
g-epoxy sulfones, are not easily available through traditional
methods. The preparation usually takes several steps and involves
hazardous reagents.11b With the products of [2,3]-sigmatropic
rearrangement of sulfur ylide, we developed an alternative syn-
thesis of g-epoxy sulfones by the direct oxidation of some of the
rearrangement products by m-CPBA. To our delight, the reaction of
the selected compounds (3a, o, r) proceeded smoothly to give the
Entry
R
Product 5
Yieldb (%)
1
2
3
3,5-(CH3O)2C6H3
p-PhC6H4
p-MeO2CC6H4
5a
5b
5c
70
40
26
corresponding
the synthesis of the corresponding cyclobutenones 8aec was suc-
cessfully achieved by Durst’s methods. Moreover, the -epoxy
g-epoxy sulfones in excellent yields. Subsequently,
a
All reactions were carried out with N-tosylhydrazones 1 (0.5 mmol, 1.0 equiv),
Rh2(OAc)4 (0.005 mmol, 1 mol %), and Cs2CO3 (0.75 mmol, 1.5 equiv) in 5 mL of 1,4-
dioxane, with addition of propargyl phenyl sulfide 4 (1.25 mmol, 2.5 equiv), fol-
lowed by stirring for 3 h at 90 ꢀC.
g
sulfones could be transformed into cyclopropanes with the aid of
LDA as base by only one step with Durst’s protocol, as exemplified
by the synthesis of 9aec (Scheme 3).
b
Isolated yields after column chromatography.
As for the electron-donating substituents on aromatic ring, such
as methyl and methoxy groups, the outcomes were satisfactory
regardless of the relative position and the number of the sub-
stituents on the aromatic ring (entries 10, 11, 13, and 14). However,
it was rather surprising to note that the reaction with p-CH3OC6H4
substituent gave low yield (entry 12), presumably due to the ex-
tremely electron-rich feature of the substrate. Substrates bearing
naphthyl (entry 15) and furyl groups (entry 16) were also exam-
ined. And the former gave the product in excellent yield while the
result of the latter was poor. Finally, it is noteworthy that the
substrate possessing cinnamenyl also undergoes the rearrange-
ment smoothly with moderate yield (entry 17).
In addition, we have examined the [2,3]-sigmatropic rear-
rangement between ketone N-tosylhydrazones and allyl phenyl
sulfide. However, no expected products could be detected and both
reactants remained intact. This may be due to the fact that the [2,3]-
sigmatropic rearrangement is sensitive to the steric interaction of
carbon anion on sulfur ylide.
Subsequently, the reaction condition was applied to the reaction
between N-tosylhydrazones and propargyl phenyl sulfide. For vari-
ous substituted N-tosylhydrazones, the reaction went smoothly and
afforded the corresponding products in moderate yields as de-
termined by the GCeMS. However, only three examples of this re-
action have been shown in Table 3 due to the difficulties in
separation. Nevertheless, these few examples provide proof that this
kind of [2,3]-sigmatropic rearrangement of sulfur ylides is applicable
for propargyl sulfide. Among these three examples, the reaction of N-
tosylhydrazone containing 3,5-(CH3O)2C6H3 underwent efficiently
and afforded the allene product 5a in good yield (entry 1). The sub-
strate bearing p-PhC6H4 could also react but gave the product in
moderate yield (entry 2). However, the yield decreases considerably
when the substituent is electron-withdrawing (entry 3).
In order to further explore the scope of the rearrangement re-
action we have prepared the allylic sulfide 6, of which the terminal
olefin is blocked by two methyl groups. Then its reactivity in the
rearrangement was tested. To our delight, the sulfide reacted
readily with N-tosylhydrazones 1a and afforded the expected
product 3r (Scheme 2).
Scheme 3. The synthesis of
based on the rearrangement products.
g-epoxy sulfones, cyclobutenones, and cyclopropanes
3. Summary
In summary, we have successfully introduced N-tosylhydrazones
into the catalytic [2,3]-sigmatropic rearrangement of sulfur ylides.
To the best of our knowledge, this is the first report on the appli-
cation of N-tosylhydrazones in DoyleeKirmse reaction. The catalytic
reaction is highly efficient and affords the products in moderate to
good yields. The reaction has excellent functional group compati-
bility and can be applied to both allylic and propargyl sulfides. In
addition, the direct oxidation of the rearrangement products,
combined with Durst’s methodology, offers a novel and convenient
approach to the synthesis of cyclobutenones and cyclopropanes.
4. Experimental section
4.1. General
All reactions with moisture and air sensitive components are
performed under a nitrogen atmosphere.1,4-Dioxane, pentane, and
ether were distilled from Na before use. 200e300 mesh silica gel
was employed for the column chromatography. The boiling point of
petroleum ether was between 60 and 90 ꢀC. 1H NMR (400 MHz) and
13C NMR (100 MHz) spectra were recorded on a Bruker-400 ARX
spectrometer. Chemical shifts were reported in parts per million
Scheme 2. Reaction of sulfide 6 with N-tosylhydrazones 1a.
Finally, we proceeded to explore the utility of the rearrangement
products. Through a survey of the literature we noted that the
rearrangement products 3aer are useful intermediates in organic
synthesis. For example, in 1970s Durst and co-worker developed

Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
5237
relative to the internal standard tetramethylsilane (
d
¼0 ppm) for 1H
MS (m/z, relative intensity): 318 (Mþ, 11), 277 (95), 197 (39), 130
(100), 115 (25); HRMS (ESI) calcd for C16H15BrNaS [MþNa]þ:
340.9976, found: 340.9971.
NMR and deuteriochloroform (
d
¼77.00 ppm) for 13C NMR spec-
troscopy. Mass spectra were determined on a VG ZAB-HS mass
spectrometer. IR was recorded with a Nicolet Avatar 330 FT-IR in-
frared spectrometer.
N-Tosylhydrazones and sulfides were prepared according to
literature procedure.8,10b,12 Materials obtained from commercial
suppliers were used without further purification unless otherwise
4.3.4. (1-(3-Bromophenyl)but-3-enyl)(phenyl)sulfane
(3d). Yield
65%; colorless oil; 1H NMR (400 MHz, CDCl3)
d
2.59e2.72 (m, 2H),
4.11 (t, J¼8.0 Hz, 1H), 5.00e5.05 (m, 2H), 5.64e5.74 (m, 1H),
7.06e7.24 (m, 7H), 7.31 (d, J¼7.6 Hz, 1H), 7.36 (s, 1H); 13C NMR
noted. The syntheses of cyclobutenones and cyclopropane from
g-
(100 MHz, CDCl3) d 40.1, 52.7, 117.6, 122.3, 126.5, 127.4, 128.7, 129.7,
epoxy sulfones have been referred to the procedures reported in
130.2, 130.8, 132.7, 133.9, 134.6, 143.8; IR (film) 668, 690, 909, 1072,
the literature.11a,c
3075 cmꢂ1; EI-MS (m/z, relative intensity): 318 (Mþ, 9), 277 (78),
79
197 (22), 130 (100), 115 (23); HRMS (ESI) calcd for C16
H BrNaS
15
4.2. Experimental procedure for the preparation of allyl
phenyl sulfides or propargyl phenyl sulfides
[MþNa]þ: 340.9976, found: 340.9975.
4.3.5. (1-(4-Bromophenyl)but-3-enyl)(phenyl)sulfane (3e). Yield 78%;
yellow oil; 1H NMR (400 MHz, CDCl3)
2.58e2.73 (m, 2H), 4.12e4.15
To a flame-dried flask, a suspension of 80% NaH (0.1 mol) in THF
(100 mL) was added and stirred at 0 ꢀC under water-ice bath. The
thiophenol (6.8 mL, 0.067 mol) was then added dropwise to the
mixture over 20 min. After completion of the addition, the water-
ice bath was removed and the mixture was allowed to warm to
room temperature and stirred for 0.5 h. Subsequently, the mixture
was again cooled to 0 ꢀC and allyl bromide or propargyl bromide
(0.1 mol) was added dropwise while stirring. After addition, the
mixture was warmed to room temperature and then stirred for 2 h.
Finally, 50 mL of satd NH4Cl solution was added to quench the
reaction. The organic layer was washed with water (2ꢁ30 mL),
extracted with Et2O (2ꢁ10 mL). The organic layers were combined
and concentrated under vacuum. The crude product was purified
by silica gel column chromatography (petroleum ether) to afford
the allyl phenyl sulfide as colorless oil.
d
(m, 1H), 5.00e5.04 (m, 2H), 5.63e5.74 (m, 1H), 7.09 (d, J¼8.4 Hz, 2H),
7.18e7.24 (m, 5H), 7.36 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
40.2, 52.6, 117.6, 120.8, 127.4, 128.7, 129.5, 131.3, 132.7, 134.1, 134.7,
140.5; IR (film) 691, 833, 909, 1010, 3075 cmꢂ1; EI-MS (m/z, relative
intensity): 318 (Mþ, 7), 277 (46), 209 (30), 130 (100), 115 (22); HRMS
79
81
(EI) calcd for C16
H H BrS
BrS [M]þ: 318.0078, found: 318.0082; C16
1
5
1
5
[M]þ: 320.0057, found: 320.0062.
4.3.6. (1-(4-Chlorophenyl)but-3-enyl)(phenyl)sulfane (3f). Yield 74%;
colorless oil; 1H NMR (400 MHz, CDCl3)
2.59e2.73 (m, 2H),
4.13e4.17 (m, 1H), 5.00e5.05 (m, 2H), 5.64e5.74 (m, 1H), 7.14e7.25
(m, 9H); 13C NMR (100 MHz, CDCl3)
40.3, 52.6, 117.5, 127.4, 128.4,
d
d
128.7, 129.2, 132.7, 134.1, 134.7, 140.0; IR (film) 691, 835, 917, 1025,
3076 cmꢂ1; EI-MS (m/z, relative intensity): 274 (Mþ, 7), 233 (61),165
35
(100), 129 (57), 109 (16); HRMS (EI) calcd for C16
274.0583, found: 274.0586.
H
ClS [M]þ:
15
4.3. Typical procedure for the Rh2(OAc)4-catalyzed [2,3]-
sigmatropic rearrangement
4.3.7. (1-(3,4-Dichlorophenyl)but-3-enyl)(phenyl)sulfane (3g). Yield
71%; colorless oil; 1H NMR (400 MHz, CDCl3)
2.59e2.68 (m, 2H),
A 50 mL flame-dried Schlenk flask was evacuated and backfilled
with N2 for three times, N-Tosylhydrazones (0.5 mmol), Rh2(OAc)4
(0.005 mmol), and 1,4-dioxane (5 mL) were charged followed by
addition of the sulfide (1.25 mmol). The mixture was heated to
90 ꢀC and stirred for 3 h. The mixture was then cooled down to
room temperature and the reaction mixture was allowed to pass
d
4.08e4.12 (m, 1H), 5.01 (s, 1H), 5.04 (d, J¼6.0 Hz, 1H), 5.64e5.69 (m,
1H), 7.03 (dd, J¼2.0, 8.2 Hz, 1H), 7.19e7.25 (m, 5H), 7.28e7.30 (m,
2H); 13C NMR (100 MHz, CDCl3)
d 40.0, 52.3, 117.9, 127.2, 127.6,
128.8, 129.7, 130.1, 130.9, 132.2, 132.8, 133.6, 134.3, 141.9; IR (film)
691, 823, 910, 1030, 3076 cmꢂ1; EI-MS (m/z, relative intensity): 308
through
a
silica plug (washed with petroleum ether/ethyl
(Mþ, 17), 267 (100), 199 (63), 164 (53), 129 (42); HRMS (EI) calcd for
35
acetate¼3:1). The resulting filtrate was concentrated under vac-
uum and the residue was purified by silica gel column chroma-
tography (petroleum ether) to give the product.
C16H
Cl2S [M]þ: 308.0193, found: 308.0197.
14
4.3.8. Methyl 4-(1-(phenylthio)but-3-enyl)benzoate (3h). Yield 71%;
yellow oil; 1H NMR (400 MHz, CDCl3)
2.63e2.77 (m, 2H), 3.87 (s,
d
4.3.1. Phenyl(1-phenylbut-3-enyl)sulfane (3a).12 Yield 81%; color-
3H, OCH3), 4.19e4.23 (m, 1H), 5.00e5.05 (m, 2H), 5.66e5.73 (m,
1H), 7.16e7.22 (m, 5H), 7.27 (d, J¼8.4 Hz, 2H), 7.92 (d, J¼8.4 Hz, 2H);
less oil; 1H NMR (400 MHz, CDCl3)
d
2.67e2.71 (m, 2H), 4.19 (t,
J¼7.6 Hz, 1H), 4.98e5.05 (m, 2H), 5.68e5.75 (m, 1H), 7.17e7.26 (m,
10H); 13C NMR (100 MHz, CDCl3)
40.4, 53.3, 117.2, 127.1, 127.2,
13C NMR (100 MHz, CDCl3)
d 40.0, 52.0, 53.0, 117.6, 127.4, 127.8,
d
128.7, 128.8, 129.5, 132.8, 133.8, 134.5, 146.8, 166.7; IR (film) 692,
732, 909, 1436, 1720 cmꢂ1; EI-MS (m/z, relative intensity): 298 (Mþ,
13), 257 (100), 189 (25), 129 (58), 115 (19), 59 (20); HRMS (ESI) calcd
for C18H19O2S [MþH]þ: 299.1106, found: 299.1100; C18H18NaO2S
[MþNa]þ: 321.0925, found: 321.0923.
127.8, 128.3, 128.6, 132.5, 134.8, 135.2, 141.5.
4.3.2. (1-(4-Nitrophenyl)but-3-enyl)(phenyl)sulfane (3b). Yield 75%;
yellow oil; 1H NMR (400 MHz, CDCl3)
d 2.54e2.72 (m, 2H), 4.15e4.19
(m, 1H), 4.93e4.98 (m, 2H), 5.58e5.65 (m, 1H), 7.08e7.17 (m, 5H),
7.24e7.27 (m, 2H), 7.98e8.02 (m, 2H); 13C NMR (100 MHz, CDCl3)
4.3.9. (1-(Biphenyl-4-yl)but-3-enyl)(phenyl)sulfane (3i). Yield 81%;
d
39.8, 52.8, 118.1, 123.5, 127.9, 128.6, 128.9, 133.1, 134.0, 146.8, 149.3;
white solid; mp 60e62 ꢀC; 1H NMR (400 MHz, CDCl3)
d 2.71e2.75
IR (film) 692, 747, 1346, 1519, 2925 cmꢂ1; EI-MS (m/z, relative in-
tensity): 285 (Mþ, 10), 244 (100), 197 (10), 130 (33), 115 (18); HRMS
(ESI) calcd for C16H15NNaO2S [MþNa]þ: 308.0721, found: 308.0719.
(m, 2H), 4.22e4.26 (m, 1H), 5.01e5.08 (m, 2H), 5.70e5.81 (m, 1H),
7.11e7.22 (m, 3H), 7.28e7.34 (m, 5H), 7.39e7.43 (m, 2H), 7.48e7.50
(m, 2H), 7.56e7.58 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 40.3, 52.9,
117.3, 126.9, 127.0, 127.1, 127.2, 128.2, 128.7, 132.5, 135.1, 139.9, 140.5,
140.7; IR (film) 695, 843, 908, 1485, 3028 cmꢂ1; EI-MS (m/z, relative
intensity): 316 (Mþ, 6), 275 (18), 207 (100),179 (40),165 (94); HRMS
(ESI) calcd for C22H20NaS [MþNa]þ: 339.1183, found: 339.1181.
4.3.3. (1-(2-Bromophenyl)but-3-enyl)(phenyl)sulfane (3c). Yield 76%;
colorless oil; 1H NMR (400 MHz, CDCl3)
d
2.67 (t, J¼7.2 Hz, 2H), 4.86
(t, J¼7.6 Hz, 1H), 5.00e5.06 (m, 2H), 5.70e5.80 (m, 1H), 7.02e7.06
(m, 1H), 7.14e7.28 (m, 6H), 7.47e7.50 (m, 2H); 13C NMR (100 MHz,
CDCl3)
d
39.9, 50.7, 117.6, 124.6, 127.0, 127.6, 128.5, 128.7, 129.1, 131.9,
4.3.10. Phenyl(1-o-tolylbut-3-enyl)sulfane (3j). Yield 85%; colorless
132.7, 134.3, 134.5, 140.3; IR (film) 661, 737, 912,1024, 3074 cmꢂ1; EI-
oil; 1H NMR (400 MHz, CDCl3)
d 2.29 (s, 3H, ArCH3), 2.70 (t,

5238
Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
J¼8.0 Hz, 2H), 4.45 (t, J¼7.6 Hz, 1H), 4.96e5.04 (m, 2H), 5.65e5.75
(m, 1H), 7.10e7.28 (m, 8H), 7.34 (d, J¼7.2 Hz, 1H); 13C NMR
133.4, 134.8, 141.8, 153.7; IR (film) 692, 733, 909, 1010, 1439 cmꢂ1
;
EI-MS (m/z, relative intensity): 230 (Mþ, 13), 121 (100), 103 (44), 91
(37), 77 (34); HRMS (ESI) calcd for C14H15OS [MþH]þ: 231.0844,
found: 231.0834.
(100 MHz, CDCl3)
d 19.5, 39.8, 48.5, 117.1, 126.2, 126.9, 127.0, 127.3,
128.7, 130.2, 132.8, 134.6, 135.3, 135.8, 139.0; IR (film) 692, 740, 915,
1025, 3074 cmꢂ1; EI-MS (m/z, relative intensity): 254 (Mþ, 5), 213
(54), 145 (100), 129 (23), 115 (18), 105 (23), 91 (18); HRMS (ESI)
calcd for C17H18NaS [MþNa]þ: 277.1027, found: 277.1022.
4.3.17. (E)-Phenyl(1-phenylhexa-1,5-dien-3-yl)sulfane
(3q). Yield
48%; yellow oil; 1H NMR (400 MHz, CDCl3)
d
2.46e2.59 (m, 2H),
3.75e3.81 (m, 1H), 5.07e5.14 (m, 2H), 5.82e5.93 (m, 1H), 6.04e6.18
(m, 2H), 7.17e7.26 (m, 8H), 7.41 (dd, J¼1.6, 8.0 Hz, 2H); 13C NMR
4.3.11. Phenyl(1-m-tolylbut-3-enyl)sulfane (3k). Yield 66%; color-
less oil; 1H NMR (400 MHz, CDCl3)
d
2.28 (s, 3H, ArCH3), 2.68 (t,
(100 MHz, CDCl3) d 39.0, 51.8, 117.3, 126.3, 127.4, 128.4, 128.7, 129.8,
J¼7.2 Hz, 2H), 4.15 (t, J¼7.6 Hz, 1H), 4.97e5.04 (m, 2H), 5.67e5.74
131.1, 133.5, 134.1, 134.9, 136.7; IR (film) 691, 748, 909, 1025,
3026 cmꢂ1; EI-MS (m/z, relative intensity): 266 (Mþ, 3), 225 (38),
157 (14), 115 (100), 91 (28); HRMS (ESI) calcd for C18H19S [MþH]þ:
267.1208, found: 267.1206.
(m, 1H), 6.99e7.05 (m, 3H), 7.12e7.19 (m, 4H), 7.25e7.27 (m, 2H);
13C NMR (100 MHz, CDCl3)
d 21.4, 40.4, 53.1, 117.1, 124.8, 127.0, 127.9,
128.1,128.5, 128.6, 132.3, 134.9, 135.2, 137.8, 141.2; IR (film) 692, 913,
1025, 1438, 3075 cmꢂ1; EI-MS (m/z, relative intensity): 254 (Mþ, 9),
213 (60), 145 (100), 129 (27), 115 (18), 105 (27); HRMS (ESI) calcd for
C17H18NaS [MþNa]þ: 277.1027, found: 277.1021.
4.3.18. (2,2-Dimethyl-1-phenylbut-3-enyl)(phenyl)sulfane
(3r). Yellow oil; 1H NMR (400 MHz, CDCl3)
d 1.10 (s, 3H), 1.20 (s,
3H), 4.04 (s, 1H), 4.97e5.07 (m, 2H), 5.99e6.06 (dd, J¼6.4, 10.8 Hz,
4.3.12. (1-(4-Methoxyphenyl)but-3-enyl)(phenyl)sulfane
1H), 7.03e7.11 (m, 3H), 7.15e7.23 (m, 5H), 7.32 (d, J¼7.2 Hz, 2H); 13C
(3l).12 Yield 18%; yellow oil; 1H NMR (400 MHz, CDCl3)
d
2.64e2.67
NMR (100 MHz, CDCl3) d 25.0, 26.8, 41.6, 65.1, 112.5, 126.2, 126.8,
(m, 2H), 3.77 (s, 3H, OCH3), 4.16e4.19 (m, 1H), 4.98e5.04 (m, 2H),
127.4, 128.5, 129.8, 130.9, 136.5, 140.4, 145.3; IR (film) 690, 737, 915,
5.67e5.71 (m, 1H), 6.78e6.80 (m, 2H), 7.15e7.27 (m, 5H); 13C NMR
1480, 2965 cmꢂ1; EI-MS (m/z, relative intensity): 268 (Mþ, 2), 199
(100 MHz, CDCl3)
d
40.5, 52.5, 55.2, 113.6, 117.1, 127.0, 128.6, 128.9,
(100), 165 (12), 117 (17), 91 (13); HRMS (ESI) calcd for C18H19S
132.4, 133.3, 134.8, 135.2, 158.6; IR (film) 692, 732, 909, 1436,
1720 cmꢂ1; EI-MS (m/z, relative intensity): 270 (Mþ, 3), 229 (5), 161
(100), 146 (11), 91 (15); HRMS (ESI) calcd for C17H18NaOS [MþNa]þ:
293.0976, found: 293.0972.
[MꢂH]þ: 267.1207, found: 267.1202.
4.3.19. (1-(3,5-Dimethoxyphenyl)buta-2,3-dienyl)(phenyl)sulfane
(5a). Yield 70%; yellow oil; 1H NMR (400 MHz, CDCl3)
3.76 (s,
d
6H, OCH3), 4.60e4.64 (m, 1H), 4.71e4.76 (m, 2H), 5.43e5.49 (m,
1H), 6.35 (t, J¼2.4 Hz, 1H), 6.52 (d, J¼2.4 Hz, 2H), 7.24e7.26 (m,
4.3.13. (1-(2,6-Dimethylphenyl)but-3-enyl)(phenyl)sulfane
(3m). Yield 88%; colorless oil; 1H NMR (400 MHz, CDCl3)
d
2.09 (s,
3H), 7.37e7.39 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 53.1, 55.3,
3H, ArCH3), 2.62 (s, 3H, ArCH3), 2.74e2.92 (m, 2H), 4.63e4.68 (m,
1H), 4.91e5.05 (m, 2H), 5.59e5.69 (m, 1H), 6.89 (d, J¼4.4 Hz, 1H),
7.01 (d, J¼4.8 Hz, 2H), 7.21e7.23 (m, 3H), 7.33e7.36 (m, 2H); 13C
92.1, 100.0, 105.7, 127.4, 128.6, 132.9, 134.8, 142.4, 160.7, 208.4; IR
(film) 692, 909, 1066, 1461, 2560 cmꢂ1; EI-MS (m/z, relative in-
tensity): 298 (Mþ, 98), 283 (100), 267 (19), 207 (38), 189 (21), 161
(33); HRMS (ESI) calcd for C18H19O2S [MþH]þ: 299.1106, found:
299.1100.
NMR (100 MHz, CDCl3)
d 21.4, 21.5, 38.8, 49.8, 116.6, 126.8, 127.4,
128.0, 128.7, 130.4, 133.2, 135.7, 135.8, 136.2, 137.2, 137.4; IR (film)
692, 769, 909, 1025, 2976 cmꢂ1; EI-MS (m/z, relative intensity): 268
(Mþ, 5), 227 (55), 159 (100), 144 (25), 129 (22); HRMS (ESI) calcd for
C18H20NaS [MþNa]þ: 291.1183, found: 291.1179.
4.3.20. (1-(Biphenyl-4-yl)buta-2,3-dienyl)(phenyl)sulfane
(5b). Yield 40%; yellow solid; mp 52e54 ꢀC; 1H NMR (400 MHz,
CDCl3)
d
4.61e4.65 (m, 1H), 4.72e4.77 (m, 1H), 4.86 (d, J¼8.4 Hz,
4.3.14. (1-(3,5-Dimethoxyphenyl)but-3-enyl)(phenyl)sulfane
1H), 5.53 (dd, J¼6.8, 8.0 Hz, 1H), 7.21e7.25 (m, 3H), 7.32 (t, J¼7.2 Hz,
(3n). Yield 74%; colorless oil; 1H NMR (400 MHz, CDCl3)
d 2.67 (t,
1H), 7.38e7.43 (m, 6H), 7.52e7.58 (m, 4H); 13C NMR (100 MHz,
J¼7.2 Hz, 2H), 3.73 (s, 6H, OCH3), 4.11 (t, J¼7.6 Hz, 1H), 5.00e5.07
CDCl3) d 52.6, 92.2, 127.0, 127.2, 127.3, 127.4, 128.2, 128.6, 128.7,
(m, 2H), 5.70e5.77 (m, 1H), 6.31 (t, J¼2.4 Hz, 1H), 6.41 (d, J¼2.0 Hz,
133.0, 134.9, 139.2, 140.4, 140.7, 208.6; IR (film) 752, 1240, 1486,
1738, 1952 cmꢂ1; EI-MS (m/z, relative intensity): 314 (Mþ, 6), 258
(94), 205 (100), 155 (36), 127 (67), 77 (44); HRMS (ESI) calcd for
C22H19S [MþH]þ: 315.1207, found: 315.1202.
2H), 7.19e7.30 (m, 5H); 13C NMR (100 MHz, CDCl3)
d 40.4, 53.4, 55.2,
99.2, 105.8, 117.2, 127.1, 128.7, 132.3, 135.1, 143.8, 160.6; IR (film) 691,
733, 909, 1065, 2936 cmꢂ1; EI-MS (m/z, relative intensity): 300 (Mþ,
22), 259 (50), 191 (100), 176 (9), 160 (10); HRMS (ESI) calcd for
C18H20NaO2S [MþNa]þ: 323.1082, found: 323.1081.
4.3.21. Methyl 4-(1-(phenylthio)buta-2,3-dienyl)benzoate (5c).
Yield 26%; yellow oil; 1H NMR (400 MHz, CDCl3)
d 3.90 (s, 3H,
4.3.15. (1-(Naphthalen-2-yl)but-3-enyl)(phenyl)sulfane (3o). Yield
OCH3), 4.63e4.68 (m, 1H), 4.74e4.79 (m, 1H), 4.83 (d, J¼8.4 Hz, 1H),
5.49 (dd, J¼6.4, 8.4 Hz, 1H), 7.23e7.25 (m, 3H), 7.32e7.34 (m, 2H),
7.39 (d, J¼8.0 Hz, 2H), 7.96 (d, J¼8.4 Hz, 2H); 13C NMR (100 MHz,
84%; colorless oil; 1H NMR (400 MHz, CDCl3)
d 2.76e2.80 (m, 2H),
4.33e4.36 (t, J¼7.6 Hz, 1H), 4.96e5.07 (m, 2H), 5.68e5.78 (m, 1H),
7.12e7.16 (m, 3H), 7.23e7.26 (m, 2H), 7.40e7.42 (m, 2H), 7.48 (dd,
J¼1.6, 8.8 Hz, 1H), 7.55 (s, 1H), 7.69e7.71 (m, 1H), 7.76e7.78 (m,
CDCl3) d 52.0, 52.6, 91.7, 127.7, 127.9, 128.7, 129.3, 129.7, 133.2, 134.2,
145.5, 166.7, 208.6; IR (film) 749, 1111, 1279, 1721, 1952 cmꢂ1; EI-MS
(m/z, relative intensity): 296 (Mþ, 100), 265 (74), 205 (11), 178 (65),
117 (18); HRMS (ESI) calcd for C18H16NaO2S [MþNa]þ: 319.0769,
found: 319.0757.
2H); 13C NMR (100 MHz, CDCl3)
d 40.3, 53.4, 125.7, 125.8, 126.0,
126.7, 127.1, 127.6, 127.7, 128.2, 128.6, 132.5, 132.6, 133.1, 134.6,
135.0, 138.7; IR (film) 691, 737, 911, 1438, 3057 cmꢂ1; EI-MS (m/z,
relative intensity): 290 (Mþ, 8), 249 (15), 181 (100), 165 (38), 153
(9); HRMS (ESI) calcd for C20H18NaS [MþNa]þ: 313.1027, found:
313.1026.
4.4. Typical procedure for the oxidation of rearrangement
products 3a, o, r to
g-epoxy sulfones
4.3.16. 2-(1-(Phenylthio)but-3-enyl)furan (3p). Yield 18%; yellow
To flask were added phenyl(1-phenylbut-3-enyl)sulfane
a
oil; 1H NMR (400 MHz, CDCl3)
d
2.62e2.77 (m, 2H), 4.22e4.26 (m,
(240 mg, 1.0 mmol) and dichloromethane (10 mL). After the sulfane
was fully dissolved, m-CPBA (90%, 0.67 g, 3.5 mmol) was slowly
added to the flask. The solution was then heated and refluxed
overnight. After the completion of the oxidation as monitored by
1H), 5.03e5.11 (m, 2H), 5.74e5.84 (m, 1H), 5.98 (d, J¼3.2 Hz, 1H),
6.23 (q, J¼1.6 Hz, 1H), 7.23e7.30 (m, 5H), 7.35 (q, J¼0.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3)
d 37.8, 46.2, 107.5, 110.1, 117.4, 127.6, 128.7,

Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
5239
TLC, the solution was first allowed to cool down to room temper-
ature and washed with 10% NaOH (aq) (2ꢁ10 mL) and H2O
(2ꢁ10 mL). The organic layer of the mixture was subsequently dried
with Na2SO4 and concentrated under vacuum. The residue was fi-
nally purified by silica gel column chromatography (petroleum
product 8 was further purified by silica gel flash chromatography
(petroleum ether/ethyl acetate¼4:1) to give a colorless oil.
4.5.1. 3-Phenylcyclobut-2-enone (8a).11a Yield 58%; colorless oil; 1H
NMR (400 MHz, CDCl3)
d 3.54 (s, 2H), 6.38 (s, 1H), 7.50e7.52 (m,
ether/ethyl acetate¼5:1) to give the
g-epoxy sulfone.
3H), 7.62e7.64 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 48.5, 128.8,
128.9, 129.7, 131.3, 131.9, 171.0, 187.4.
4.4.1. 2-(2-Phenyl-2-(phenylsulfonyl)ethyl)oxirane
(7a).11c Yield
96%; white solid; mp 108e110 ꢀC; 1H NMR (400 MHz, CDCl3)
2.32e2.43 (m, 1H), 2.47e2.52 (m, 1H), 2.56e2.63(m, 1H),
2.67e2.73(m, 1H), 4.30e4.34(m, 2H), 7.09e7.30 (m, 5H), 7.35e7.40
(m, 2H), 7.49e7.56 (m, 3H); 13C NMR (100 MHz, CDCl3)
31.1, 47.9,
4.5.2. 3-(Naphthalen-2-yl)cyclobut-2-enone (8b). Yield 52%; color-
less oil; 1H NMR (400 MHz, CDCl3)
3.63 (s, 2H), 6.46 (s, 1H),
7.57e7.63 (m, 2H), 7.71e7.73 (m, 1H), 7.87e7.94 (m, 3H), 7.99 (s,
1H); 13C NMR (100 MHz, CDCl3)
48.6, 124.3, 127.1, 127.9, 128.4,
d
d
d
d
50.3, 68.5, 128.4, 128.5, 128.6, 128.9, 129.0, 129.6, 129.8, 131.5, 132.3,
133.6, 136.8.
128.8, 128.9, 129.1, 130.0, 130.2, 132.8, 134.6, 170.7, 187.5; IR (film)
750, 817, 1051, 1553, 1750 cmꢂ1; EI-MS (m/z, relative intensity): 194
(Mþ, 72), 165 (100), 127 (10), 115 (10), 39 (12); HRMS (ESI) calcd for
C14H11O [MþH]þ: 195.0810, found: 195.0805, C14H10NaO [MþNa]þ:
217.0629, found: 217.0624.
4.4.2. 2-(2-(Naphthalen-2-yl)-2-(phenylsulfonyl)ethyl)oxirane
(7b). Yield 91%; white solid; mp 92e94 ꢀC; 1H NMR (400 MHz,
CDCl3)
d 2.37e2.44 (m, 1H), 2.51e2.53 (m, 1H), 2.64e2.66 (m, 1H),
2.68e2.76 (m, 2H), 4.47e4.50 (m, 1H), 7.30e7.34 (m, 3H), 7.48e7.55
4.5.3. 4,4-Dimethyl-3-phenylcyclobut-2-enone (8c). Yield 32%; col-
(m, 5H), 7.60 (s, 1H), 7.69e7.81 (m, 3H); 13C NMR (100 MHz, CDCl3)
orless oil; 1H NMR (400 MHz, CDCl3)
d
1.42 (s, 6H), 6.18 (s, 1H),
d
31.3, 47.9, 49.2, 68.7, 126.4, 126.4, 126.7, 127.6, 128.0, 128.4, 128.6,
7.41e7.43 (m, 3H), 7.54e7.56 (m, 2H); 13C NMR (100 MHz, CDCl3)
128.9,129.9, 132.9, 133.3,133.6, 136.9; IR (film) 699, 738, 1025,1480,
2931 cmꢂ1; EI-MS (m/z, relative intensity): 338 (Mþ, 30), 196 (40),
153 (100), 128 (48), 77 (80); HRMS (ESI) calcd for C20H19O3S
[MþH]þ: 339.1055, found: 339.1048, C20H18NaO3S [MþNa]þ:
361.0874, Found: 361.0876.
d 21.1, 62.2, 126.3, 128.7, 129.1, 130.6, 131.8, 180.9, 196.4; IR (film)
689, 771, 1150, 1558, 1754 cmꢂ1. EI-MS (m/z, relative intensity): 172
(Mþ, 75), 157 (43), 143 (22), 129 (100), 77 (38); HRMS (ESI) calcd for
C12H13O [MþH]þ: 173.0966, found: 173.0961, C12H12NaO [MþNa]þ:
195.0786, found: 195.0780.
4.4.3. 2-(2-Methyl-1-phenyl-1-(phenylsulfonyl)propan-2-yl)oxirane
4.6. Typical procedure for the synthesis of cyclopropanes 9
(7c). Yield 90%; white solid; mp 75e76 ꢀC; 1H NMR (400 MHz,
CDCl3)
d
1.31 (m, 3H), 1.33 (m, 3H), 2.62e2.69 (m, 2H), 3.16e3.17 (m,
To a 25 mL flame-dried Schlenk tube were added g-epoxy sul-
1H), 4.08 (s, 1H), 6.51 (d, J¼7.6 Hz, 1H), 6.96 (t, J¼7.6 Hz, 1H)
fone 7 (1.0 mmol) and 2 mL THF. The flask was evacuated and
backfilled with N2 for three times and cooled to ꢂ30 ꢀC. LDA
(1.2 mmol, 2.0 M in THF) was added dropwise via syringe under
stirring. The reaction mixture was kept at ꢂ30 ꢀC for 0.5 h, allowed
to warm to room temperature and then stirred for an additional
0.5 h. Satd NH4Cl solution was added to quench the reaction. The
mixture was extracted with CH2Cl2 (3ꢁ10 mL) and the organic layer
was separated, dried over Na2SO4, and concentrated under vacuum.
Subsequent silica gel flash chromatography (petroleum ether/ethyl
acetate¼2:1) gives the product 9 as a white solid.
7.19e7.27 (m, 4H), 7.34e7.47 (m, 3H), 8.01 (d, J¼8.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3)
d 21.3, 24.2, 40.1, 44.8, 57.5, 128.1, 128.2,
128.3, 128.4, 129.7, 130.8, 132.2, 132.7, 132.9, 140.0; IR (film) 669,
743, 1144, 1308, 2924 cmꢂ1; EI-MS (m/z, relative intensity): 316
(Mþ, 17), 298 (23), 175 (6), 129 (76), 77 (100); HRMS (ESI) calcd for
C18H21O3S [MþH]þ: 317.1211, found: 317.1206, C18H20NaO3S
[MþNa]þ: 339.1031, found: 339.1028.
4.5. Typical procedure for the synthesis of cyclobutenones 8
To a 50 mL flame-dried Schlenk flask were added
g
-epoxy sul-
4.6.1. (2-Phenyl-2-(phenylsulfonyl)cyclopropyl)methanol
Yield 73%; white solid; mp 131e133 ꢀC; 1H NMR (400 MHz, CDCl3)
1.58e1.61 (m, 1H), 2.03e2.11 (m, 2H), 2.86 (s, 1H), 4.30e4.35 (m,
2H), 7.11e7.12 (m, 4H), 7.18e7.19 (m, 1H), 7.30e7.49 (m, 5H); 13C
NMR (100 MHz, CDCl3) 17.9, 32.3, 52.9, 60.4, 128.1, 128.4, 128.6,
(9a).11c
fone 7 (1.0 mmol) and 15 mL THF. The flask was evacuated and
backfilled with N2 for three times and cooled to ꢂ78 ꢀC. After the
g-
d
epoxy sulfone was dissolved, methylmagnesium iodide (2.5 mmol,
2.5 M in ether) was added via syringe dropwise under stirring. The
reaction mixture was allowed to warm to room temperature and
stirred overnight. The reaction was then quenched with satd NH4Cl
(aq) and the mixture was extracted with Et2O (3ꢁ30 mL). The or-
ganic layer was collected and concentrated under vacuum. The
crude product obtained was further purified by silica gel flash
chromatography (petroleum ether/ethyl acetate¼2:1) to give
cyclobutanol as white solid.
d
128.7, 131.2, 133.3, 135.3, 138.5.
4.6.2. (2-(Naphthalen-2-yl)-2-(phenylsulfonyl)cyclopropyl)methanol
(9b). Yield 85%; white solid; mp 133e135 ꢀC; 1H NMR (400 MHz,
CDCl3)
4.30e4.43 (m, 2H), 7.18e7.26 (m, 3H), 7.41e7.48 (m, 5H), 7.58e7.64
(m, 3H), 7.73e7.75 (m, 1H); 13C NMR (100 MHz, CDCl3)
18.1, 32.4,
52.9, 60.4, 126.3, 126.8, 127.5, 127.8, 127.9, 128.4, 128.6, 128.7, 131.8,
d 1.67e1.70 (m, 1H), 2.12e2.18 (m, 2H), 2.89 (s, 1H),
d
To a 50 mL round-bottom flask were added cyclobutanol
(1.0 mmol) and 5 mL acetone. After the solid was dissolved,
1.1 equiv of Jones’ reagent was added dropwise. The oxidation was
monitored by TLC. Upon completion, excess amount of oxidizing
reagent was destroyed by addition of 10% Na2SO3 solution. The
reaction mixture was then poured into satd NH4Cl (aq) and the
mixture was extracted with CH2Cl2 (3ꢁ10 mL). The combined or-
ganic layer was dried over Na2SO4 and concentrated under vacuum
to a few milliliters. Et3N (0.5 mL) was added to the residue and the
mixture was stirred at room temperature. The reaction was moni-
tored by TLC. After completion, the resulting mixture was washed
with 5% HCl solution (2ꢁ10 mL) and the organic layer was sepa-
rated, dried over Na2SO4, and concentrated under vacuum. The
132.6, 132.8, 133.4, 138.2; IR (film) 688, 741, 1147, 1303, 3058 cmꢂ1
;
EI-MS (m/z, relative intensity): 338 (Mþ, 15), 197 (99), 154 (40), 141
(100), 77 (68); HRMS (ESI) calcd for C20H19O3S [MþH]þ: 339.1055,
found: 339.1040.
4.6.3. (2,2-Dimethyl-3-phenyl-3-(phenylsulfonyl)cyclopropyl)metha-
nol (9c). Yield 76%, colorless oil; 1H NMR (400 MHz, CDCl3)
d 0.93
(s, 3H), 1.26 (s, 1H), 1.88 (s, 3H), 2.57e2.61 (m, 1H), 3.58e3.73 (m,
2H), 6.59 (d, J¼7.6 Hz, 1H), 6.88e6.91 (m, 1H), 7.25e7.30 (m, 4H),
7.36e7.46 (m, 4H); 13C NMR (100 MHz, CDCl3)
d 21.2, 22.2, 29.4,
36.8, 59.8, 127.7, 128.1, 128.2, 128.3, 128.7, 130.9, 132.7, 132.9, 134.5,
139.6; IR (film) 688, 705, 1145, 1300, 2927 cmꢂ1; EI-MS (m/z,

5240
Y. Li et al. / Tetrahedron 68 (2012) 5234e5240
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relative intensity): 175 (14), 157 (46), 105 (48), 91 (100), 77 (87);
HRMS (ESI) calcd for C18H20NaO3S [MþNa]þ: 339.1031, found:
339.1025.
Acknowledgements
The project is supported by 973 Program (No. 2009CB825300)
NSFC and SRF for ROCS, MOE.
Supplementary data
1H and 13C NMR spectra for all the products are provided. Sup-
plementary data related to this article can be found online at
doi:10.1016/j.tet.2012.03.032.
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