A base-controlled regioselective synthesis of allyl and vinyl phenyl sulfones

Article abstract of DOI:10.1016/j.tetlet.2013.03.056

A reaction of diethyl phenylsulfonylmethylphosphonate with 2-arylacetaldehydes in the presence of a catalytic excess of sodium hydride (1.1 equiv) yields allyl phenyl sulfones in excellent yield under mild reaction conditions. In contrast, when less than 1 equiv of sodium hydride (0.90 equiv) is used, the corresponding vinyl phenyl sulfones are obtained exclusively. The vinyl phenyl sulfones can be completely converted to allyl phenyl sulfones with only 0.2 equiv of NaH, suggesting that the second hydride involvement in the above transformation is catalytic. The regioselective control observed in these reactions offers a general method for synthesizing novel vinyl and allyl phenyl sulfones in one step from the same starting materials. The regioselectivity and stereoselectivity of this reaction, however, are not maintained when 2-alkylacetaldehydes are reacted with diethyl phenylsulfonylmethylphosphonate under identical reaction conditions. Our results indicate that an extended conjugation of the double bond in allylsulfones formed from the reaction of 2-arylacetaldehydes is required for the observed regio- and stereoselectivity.

Full text of DOI:10.1016/j.tetlet.2013.03.056

Tetrahedron Letters 54 (2013) 2717–2721
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
A base-controlled regioselective synthesis of allyl and vinyl phenyl sulfones
⇑
Dibyendu Dana , Anibal R. Davalos , Gopal Subramaniam, Nisar Afzal, William H. Hersh, Sanjai Kumar
Department of Chemistry and Biochemistry, Queens College and the Graduate Center of the City University of New York, Queens, NY 11367-1597, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A reaction of diethyl phenylsulfonylmethylphosphonate with 2-arylacetaldehydes in the presence of a
catalytic excess of sodium hydride (1.1 equiv) yields allyl phenyl sulfones in excellent yield under mild
reaction conditions. In contrast, when less than 1 equiv of sodium hydride (0.90 equiv) is used, the cor-
responding vinyl phenyl sulfones are obtained exclusively. The vinyl phenyl sulfones can be completely
converted to allyl phenyl sulfones with only 0.2 equiv of NaH, suggesting that the second hydride
involvement in the above transformation is catalytic. The regioselective control observed in these reac-
tions offers a general method for synthesizing novel vinyl and allyl phenyl sulfones in one step from
the same starting materials. The regioselectivity and stereoselectivity of this reaction, however, are not
maintained when 2-alkylacetaldehydes are reacted with diethyl phenylsulfonylmethylphosphonate
under identical reaction conditions. Our results indicate that an extended conjugation of the double bond
in allylsulfones formed from the reaction of 2-arylacetaldehydes is required for the observed regio- and
stereoselectivity.
Received 2 January 2013
Revised 12 March 2013
Accepted 15 March 2013
Available online 24 March 2013
Keywords:
Allyl sulfones
Vinyl sulfones
2-Arylacetaldehyde
2-Phenylacetaldehyde
2-Phenylethanal
Vinyl phenyl sulfone
Allyl phenyl sulfone
Ó 2013 Elsevier Ltd. All rights reserved.
A diverse group of important synthetic intermediates can be
widely accessed through the chemistry of the aryl sulfonyl func-
tional group.1,2 Vinyl and allyl sulfones are important members
of this class of compounds and are used as intermediates in a vari-
ety of organic transformations.3–6 For example, vinyl aryl sulfones
have been successfully utilized to develop potent and selective
inhibitory agents and activity-based probes of cysteine prote-
ases.7,8 Similarly, allyl aryl sulfones are convenient intermediates
for synthesizing natural products, such as [(ꢀ)-erythrodiene],
squalene, and coenzyme Q10.9–11
NaH with sulfonyl methylphosphonate.15,21 Thus, 1 was treated
with 2-phenylacetaldehyde in the presence of 2.0 equiv NaH at
0 °C resulting in a quantitative conversion to allylic sulfone 9 with-
out any trace of the desired vinylic sulfone 2 (Scheme 1).22 Even
when we reduced the number of equivalents of NaH to 1.1 equiv,
only allylic sulfone 9 formed, again with no vinylic sulfone 2. The
use of 1 equiv of NaH however yielded predominantly the vinylic
sulfone 2 (4:1 vinylic:allylic mixture). Surprisingly, a further
reduction of NaH (0.9 equiv) led to exclusive formation of vinylic
sulfone 2, with no trace of the allylic sulfone 9. Importantly, all
reactions went to completion within an hour, and any additional
time of reaction did not affect either the regioselectivity of the
products or their yield. This is an interesting finding since many
of the literature methods involve significantly higher reaction times,
and often give products with compromised regioselectivity.12,13
Our efforts to ascertain the structure of 2 was hampered by pre-
viously misreported spectral characteristics of this com-
pound.13,23,24 Therefore, a complete structural analysis by NMR
was undertaken to unambiguously establish the structures of 2
and 9 (see Table 1 for complete 1H and 13C assignment for 2 and
9). The 1H–1H scalar coupling between the olefinic protons was
more than 15 Hz indicating a trans geometry for both compounds.
The relative position of the double bond with respect to the phenyl
ring was established from 1H–13C long range correlation (HMBC)
experiments (Fig. S4 and S14—Supplementary data). In addition,
we also detected NOE between methylene protons and the ortho
protons of the adjacent phenyl ring in 2 while a similar NOE was
observed between one olefinic proton and the ortho protons of
the adjacent phenyl ring in 9. A complete assignment of 1H and
Most synthetic methods for preparation of vinyl sulfones start
with an alkene or 1-haloalkene derivative and involve multiple
steps.7,12,13 One of the challenges in the synthesis of vinyl sulfones
lies in the increased preference for b,
c over a, b unsaturation. This
often leads to isomeric mixtures of vinylic and allylic sulfones.12,14
Isomerically pure vinyl sulfones are easily synthesized in systems
where b,
c
unsaturation is not possible.15 Most allylic sulfones
are either prepared by treating vinylic sulfones with a base, or by
a direct conversion of allylic alcohols or alkenes in the presence
of a metal catalyst.12,16–18 Recently, the reaction of benzylic alco-
hols with sulfinyl chlorides and arenesulfonyl cyanides with allylic
alcohols were utilized to produce allylic sulfones.19,20
In our effort to make vinyl sulfones as inhibitors of certain clas-
ses of therapeutically important enzymes, we followed established
literature protocols for analogous reactions that involved the use of
⇑
Corresponding author. Tel.: +1 718 997 4120; fax: +1 718 997 5531.
E-mail address: Sanjai.Kumar@qc.cuny.edu (S. Kumar).
These authors contributed equally to this work.
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.03.056

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D. Dana et al. / Tetrahedron Letters 54 (2013) 2717–2721
O
O
0.9 eq. NaH
S
R
2, 9: R = Phenyl
Ph
3, 10: R = biphenyl
4, 11: R = 1-naphthyl
5, 12: R = 2-methylphenyl
6, 13: R = 2-chlorophenyl
7, 14: R = 4-methylphenyl
8, 15: R = 4-methoxyphenyl
O
P
OEt
O
O
2-8
THF
0 o
S
OEt
O
Ph
R
+
C
H
O
O
S
R
1
Ph
1.1 eq. NaH
9-15
Scheme 1. Yield (calculated based on precursor aldehyde): 2 (81%), 3 (74%), 4 (71%), 5 (66%), 6 (69%), 7 (75%), 8 (73%), 9 (94%), 10 (83%), 11 (81%), 12 (81%), 13 (84%), 14 (82%),
15 (85%).
Table 1
1H and 13C NMR chemical shifts for vinyl phenyl sulfone, 2 and allyl phenyl sulfone, 9a
c'
c'
d'
d'
b'
a'
b'
a'
O
O
O
O
2
2
S
S
b
b
c
c
d
a
a
3
1
3
1
d
9
2
13C shifts (ppm)
1H shifts (ppm), J values in Hz
Compound 2
Compound 9
Compound 2
Compound 9
1
2
3
a
b
c
d
a0
b0
c0
d0
131.53
145.42
37.64
60.51
6.26 (dt, 15.1, 1.7)
7.16 (dt, 15.1, 6.5)
3.56 (dd, 6.5, 1.7)
—
3.96 (dd, 7.6, 1.2)
6.10 (dt, 15.8, 7.6)
6.36 (dt, 15.9, 1.2)
—
115.12
139.25
138.30
128.55
129.14
133.84
135.73
126.64
128.70
128.57
140.5
127.64
129.27
133.34
136.21
128.84
128.89
127.11
7.86 (dd, 8.4, 1.4)b
7.54 (tt, 7.5, 1.2)b
7.62 (tt, 7.5, 1.3)b
—
7.88 (dd, 8.2, 1.3)b
7.54 (tt, 7.5, 1.3)b
7.64 (tt, 7.5, 1.3)b
—
7.13 (dd, 8.2, 1.4)b
7.32 (tt, 7.5, 1.4)b
7.26 (tt, 7.5, 1.4)b
7.28 (m)
7.30 (m)
7.28 (m)
a
Chemical shifts were measured relative to TMS at 20 °C on a 500 MHz NMR spectrometer. Solvent is CDCl3. To make comparison of shifts easier, the numbering of carbons
is kept the same in both compounds and is shown in the structures above. Complete assignments were made using 1D 1H and 13C as well as 2D homo- and hetero-nuclear
correlation and NOESY experiments.
b
These protons exhibit second-order splitting, the appearance of which may deviate by a small extent from the pattern mentioned here depending on the spectrometer
frequency.
13C NMR peaks for 2 and 9 also established the characteristic spec-
tral differences between the , b unsaturation versus the b,
with 1 gave allyl sulfone, but a substantial amount of vinyl sulfone
was also present (Table 2). When 2.2 equiv of NaH was used, the
reaction gave allylic sulfone 19 as the major product, again with
diminished stereoselectivity. Table 2 lists the distribution of regioi-
somers with their E/Z ratios obtained for a panel of 2-alkylacetal-
dehydes. With 0.9 equiv of NaH, exclusive formation of the
vinylic sulfones was observed but again the corresponding allylic
sulfones formed with diminished regio- and stereoselectivity when
1.1 equiv of NaH was used. These results, taken together, indicate
that the base-controlled regio- and stereochemistry is sensitive
a
c
unsaturation. For example, the methylene carbon in 9 experiences
the ꢀI effect of the sulfone and is 23 ppm downfield shifted com-
pared to the methylene carbon in 2. The ꢀR effect of the sulfone
can be observed on the b olefinic carbon in 2 which is substantially
downfield shifted and observed at 145.42 ppm. The structure of 2
was also confirmed by X-ray crystallography (Fig. 1).25
After clearly establishing the structures of 2 and 9, we used six
additional arylacetaldehyde substrates to probe the generality of
the regio- and stereochemistry (Scheme 1). Thus, when a panel
of 2-arylacetaldehydes, shown in Scheme 1, were synthesized26–
to the nature of the a-substituent of the acetaldehyde.
To probe if a strong base such as NaH was essential for the ob-
served regio- and stereoselectivity, we carried out the reactions of
1 with 2-phenylacetaldehyde and 1 with butanal in the presence of
a weaker base, potassium tert-butoxide (1.1 equiv). In both cases,
the exclusive regioselectivity was lost as the reaction with 2-phe-
nylacetaldehyde yielded a 11:14 mixture of 9 and 2 while butanal
gave a 17:3 mixture of 16 and 19. To assess if a base stronger than
NaH could drive an exclusive conversion of butanal to allylic
sulfones 19, a reaction of 1 with butanal was carried out in the
31
and subsequently treated with 1 using 0.9 and 1.1 equiv of
NaH, the corresponding vinyl and allyl sulfones in high yields were
obtained with exclusive E stereochemistry. To probe the impor-
tance of aryl substitution at the 2-position of acetaldehyde, the ali-
phatic aldehyde butanal was first examined. Thus, when butanal
was allowed to react with 1 in the presence of 0.9 equiv of NaH,
only the vinylic derivative 16 was observed with diminished stere-
oselectivity (Table 2). At 1.1 equiv of NaH, a reaction of butanal

D. Dana et al. / Tetrahedron Letters 54 (2013) 2717–2721
2719
A quantitative conversion to the allylic sulfone 9 was observed. In
contrast, treatment of 9 even with 1 equiv of NaH and longer reac-
tion times did not give any conversion to 2. This suggests that
vinylic sulfone 2 is an intermediate in the formation of thermody-
namically more stable allylic sulfone 9: similarly 0.2 equiv of NaH
was also sufficient to convert vinyl sulfones 3 and 4 completely to
allyl sulfones 10 and 11. Considering the results from Table 2, it is
clear that aryl substitution at the
c position of the vinylic sulfones
plays a crucial role for regio- and stereoselectivity, and only a cat-
alytic amount of NaH is necessary for the formation of allyl sulfone
from vinyl sulfone. To gain further insight into the mechanism of
this transformation, a computational analysis was undertaken.32
Figure 1. X-ray crystal structure of 2. ORTEP40 drawing with complete numbering of
atoms, viewed approximately normal to the alkene plane.
The standard heat of formation ð
D
H0f Þ by T1 method33 as well as to-
tal energy (
D
E) by DFT methods showed that allylic sulfones 9 and
19E were thermodynamically more stable than their correspond-
ing vinylic sulfones 2 and 16E by a comparable amount [DDH0f fa-
vors 9 and 19E by ꢀ13.1 kJ/mol and ꢀ14.9 kJ/mol, respectively, and
presence of 1.1 equiv of n-butyllithium. Surprisingly, the reaction
yielded exclusively the vinyl sulfones 16, without any trace of cor-
responding allylic sulfones. This perhaps could be due to the com-
promised stability of n-butyllithium reagent in the reaction
mixture under our experimental conditions (typically 0–10 °C,
1.5 h). Thus, it appears that an optimal basicity of NaH is required
for this regio- and stereoselective transformation.
D
E favors 9 and 19E by ꢀ20.4 kJ/mol and ꢀ24.1 kJ/mol, respec-
tively]. The energy-minimized geometry for the sulfones as well
as the
DE value for the conversion of 2 to 9 agrees closely with
the estimated values reported by Lee et al.34 To understand why
only vinylic sulfone 2 would convert easily to allylic sulfone 9 with
catalytic NaH but not the vinylic sulfone 16, we compared the dif-
ferences between the neutral sulfones and the anions obtained
after proton abstraction to approximate the energy barrier for this
To understand the mechanism of formation of the allylic sulfone
9 in our synthetic procedure, 2 was treated with 0.2 equiv of NaH.
Table 2
Treatment of 1 with 2-alkylacetaldehydes under varying NaH concentrations
O
O
O
P
OEt
O
O
O
O
THF, NaH
0oC
S
R
S
R
S
OEt
O
Ph
+
Ph
Ph
R
+
16, 19 :
17, 20 :
18, 21 :
R = CH2CH3
R = CH(CH3)2
R = (CH2)4CH3
H
E, Z
16-18
E, Z
19-21
1
Percent distribution of vinyl and allyl isomers and their E/Z ratiosa
With 1.1 equiv NaH
R=
With 0.9 equiv NaH
–CH2CH3
–CH(CH3)2
–(CH2)4CH3
100% 16 (5/1), 0% 19
100% 17 (1/0), 0% 20
100% 18 (7:3), 0% 21
58% 16 (13/1), 42% 19 (2/1)
67% 17 (1/0), 33% 20 (1/1)
72% 18 (7/3), 28% 21 (1/1)
a
Peaks corresponding to each isomer were integrated and normalized from the NMR spectrum of the crude mixture. 1H NMR, 13C NMR, and mass spectrometric
characterization of 16 and 19 are included in the reference section.41 Complete characterization of NMR peaks was not carried out for compounds 17, 18, 20, and 21 as these
compounds were previously reported and characterized.42–44
SO2Ph
O
P
O
O
Ph
O
O
P
OEt
OEt
OEt
O
O
S
H
H
S
OEt
Ph
PhCH2CHO
H
Ph
H
1
OEt
Ph
22
2
HO
P
OEt
H-
O
2
SO2Ph
SO2Ph
SO2Ph
Ph
Ph
Ph
9
23
23
23
Scheme 2. Proposed mechanism of the formation of allylic sulfone 9 when catalytic excess of sodium hydride is used.

2720
D. Dana et al. / Tetrahedron Letters 54 (2013) 2717–2721
O
P
OEt
O
O
References and notes
O
O
Ph
Ph
O
THF, NaH
oC
S
Ph
Ph
S
OEt
Ph
+
Ph
1. Najera, C.; Yus, M. Tetrahedron 1999, 55, 10547.
2. Trost, B. M.; Ghadiri, M. R. J. Am. Chem. Soc. 1984, 106, 7260.
3. Trost, B. M. B. Chem. Soc. Jpn. 1988, 61, 107.
0
H
1
24
4. Magnus, P. D. Tetrahedron 1977, 33, 2019.
5. Fabre, J. L.; Julia, M.; Verpeaux, J. N. Tetrahedron Lett. 1982, 23, 2469.
6. Meadows, D. C.; Gervay-Hague, J. Med. Res. Rev. 2006, 26, 793.
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8. Wang, G.; Mahesh, U.; Chen, G. Y. J.; Yao, S. Q. Org. Lett. 2003, 5, 737.
9. Deng, K.; Chalker, J.; Yang, A.; Cohen, T. Org. Lett. 2005, 7, 3637.
10. Mohri, M.; Kinoshita, H.; Kotake, H.; Inomata, K. Chem. Lett. 1985, 451.
11. Mohri, M.; Kinoshita, H.; Inomata, K.; Kotake, H.; Takagaki, H.; Yamazaki, K.
Chem. Lett. 1986, 1177.
12. Inomata, K.; Sasaoka, S.; Kobayashi, T.; Tanaka, Y.; Igarashi, S.; Ohtani, T.;
Kinoshita, H.; Kotake, H. Bull. Chem. Soc. Jpn. 1987, 60, 1767.
13. Michrowska, A.; Bujok, R.; Harutyunyan, S.; Sashuk, V.; Dolgonos, G.; Grela, K. J.
Am. Chem. Soc. 2004, 126, 9318.
14. Inomata, K.; Kobayashi, T.; Sasaoka, S.; Kinoshita, H.; Kotake, H. Chem. Lett.
1986, 289.
15. Zhao, C.; Toste, F. D.; Bergman, R. G. J. Am. Chem. Soc. 2011, 133, 10787.
16. Tamura, R.; Hayashi, K.; Kakihana, M.; Tsuji, M.; Oda, D. Chem. Lett. 1985, 229.
17. Chandrasekhar, S.; Jagadeshwar, V.; Saritha, B.; Narsihmulu, C. J. Org. Chem.
2005, 70, 6506.
Scheme 3.
conversion. DFT calculations at the B3LYP/6-311G⁄ level showed
that the difference is lower by 41.3 kJ/mol for 2 compared to
16E. It can be inferred that the resonance stabilization of the
resulting negative charge by the aromatic ring (23—Scheme 2)
plays a dominant role in the ease with which the allylic sulfone
forms. Based on our experimental observation and computational
analysis, a plausible mechanism for the quantitative conversion
of 1 to 2 and 9 is proposed. The reaction proceeds through a cyclic
Wittig intermediate 22 which readily breaks down to yield the
vinylic sulfone 2.35 When a catalytic excess of base is present, an
acidic proton is abstracted from 2 to form a resonance-stabilized
carbanion 23. This carbanion acts as a base to abstract another pro-
ton from 1 to form the thermodynamically stable product 9, thus
regenerating carbanion 23 which can subsequently turn over an-
other substrate molecule 2. Catalytic participation of NaH has been
observed previously.36
Having established the effect of conjugation from one phenyl
moiety and to gain further support for our postulated mechanism,
we hypothesized that 2,2-diphenylacetaldehyde will form the allyl
sulfone even more favorably. We therefore synthesized 2,2-diphe-
nylacetaldehyde37 and carried out a reaction with 1 using 0.9 equiv
NaH. Not surprisingly, the reaction exclusively gave the allylic sul-
fone 2438 (Scheme 3), a compound that has been previously pre-
pared by other methods.39 When this reaction was repeated with
0.5 equiv of NaH, it still resulted in a quantitative conversion of
the 2,2-diphenyl-acetaldehyde to 24 (50% overall yield) with no
18. Aydin, J.; Larsson, J. M.; Selander, N.; Szabo, K. J. Org. Lett. 2009, 11, 2852.
19. Li, H. H.; Dong, D. J.; Jin, Y. H.; Tian, S. K. J. Org. Chem. 2009, 74, 9501.
20. Reddy, L. R.; Hu, B.; Prashad, M.; Prasad, K. Angew. Chem., Int. Ed. 2009, 48, 172.
21. Henry, C. E.; Kwon, O. Org. Lett. 2007, 9, 3069.
22. Typical procedure for synthesis of 2–8:
((phenylsulfonyl)methyl)phosphonate (500 mg, 1.7 mmol, 1 equiv) in dry
tetrahydrofuran (2 mL) was added dropwise to stirring suspension of
sodium hydride (39 mg, 1.53 mmol, 0.9 equiv) in dry tetrahydrofuran (5 mL)
at 0 °C under inert condition. After 30 min, solution of -substituted
a
solution of diethyl
a
a
a
acetaldehyde (1.7 mmol, 1.0 equiv) in dry tetrahydrofuran (3 mL) was added
to the reaction mixture. Stirring was continued for an hour. The reaction was
quenched by an addition of 5 mL of sodium bisulfate (5 wt % solution). The
solution was concentrated under vacuum, diluted with water (10 mL), and
extracted with ethylacetate (3 ꢁ 5 mL). The combined organic extracts were
washed with saturated aqueous sodium bicarbonate and brine, dried over
sodium sulfate, filtered, and concentrated under vacuum. Purification by flash
column chromatography (silica gel; 97:3 hexane/ethylacetate) provided the
desired product.
Compounds 9–15 were synthesized by following the same protocol used in the
synthesis of 2–8 except that 1.1 equiv (44.9 mg, 1.87 mmol) of NaH was used.
For the synthesis of 24, E and Z isomers of 16–21, appropriate amount of NaH
was utlized (see Table 2). The characterization of compounds is as follows:
(E)-((3-Phenylprop-1-en-1-yl)sulfonyl)benzene (2) (yield: 870 mg). [see
trace of the vinyl sulfone. Indeed the
DE calculations by DFT meth-
ods show that formation of 24 is favored by 35.9 kJ/mol over its
corresponding vinylic isomer (i.e., about twice the amount calcu-
lated for 9). Both experimental results and theoretical calculations
confirm that an extended conjugation favors the formation of the
allylic sulfones over the corresponding vinylic analogs.
In conclusion, we have described a convenient general route to
synthesize vinylic and allylic sulfones that contain an aromatic
group on the c-carbon of the sulfones. The reactions described here
proceed in just 1 h time, do not require any metal catalyst, and
yield exclusively a single product with high regio- and stereoselec-
tivity. Importantly, this can be achieved simply by changing the
amount of NaH used in the reaction mixture. Thus, while a catalytic
excess of NaH (1.1 equiv) produces the allylic sulfones in quantita-
tive yield upon reaction of 1 with 2-arylacetaldehydes, a sub-stoi-
chiometric amount of NaH (0.9 equiv) produces only the
corresponding vinylic sulfones.
Table
1
for 1H and 13C NMR assignments]. LRMS [ESI-MS +ve] calcd for
(C15H14O2S+Na): 281.1, observed: 281.3.
(E)-4-(3-(Phenylsulfonyl)allyl)-1,10-biphenyl (3). 1H NMR (400 MHz, (CDCl3)) d
ppm: 3.60 (d, J = 6.6 Hz, 2H), 6.30 (d, J = 15.2 Hz, 1H), 7.14–7.66 (m, 13H), 7.88
(m, 2H). 13C NMR (100 MHz, (CDCl3) d ppm: 37.27, 127.04, 127.39, 127.61,
127.67, 128.82, 129.28, 129.29, 131.64, 133.37, 135.21, 140.12, 140.47, 140.58,
145.30. LRMS [ESI-MS +ve] calcd for (C21H18O2S+Na): 357.1, observed: 357.2.
(E)-1-(3-(Phenylsulfonyl)allyl)naphthalene (4). 1H NMR (500 MHz, (CD3)2CO) d
ppm: 4.14 (d, J = 6.4 Hz, 2H), 6.51 (d, J = 15.1 Hz, 1H), 7.20–8.09 (m, 13H). 13C
NMR (125 MHz, (CD3)2CO)
d ppm: 34.36, 123.77, 125.71, 125.85, 126.27,
127.10, 127.35, 127.76, 128.76, 129.35, 131.68, 131.97, 133.28, 133.53, 134.07,
141.22, 145.47. LRMS [ESI-MS +ve] calcd for (C19H16O2S+Na): 331.1, observed:
331.2.
(E)-1-Methyl-2-(3-(phenylsulfonyl)allyl)benzene (5). 1H NMR (500 MHz,
CDCl3) d ppm: 2.20 (s, 3H), 3.56 (dd, J = 6.2 and 1.4 Hz, 2H), 6.13 (dt, J = 15.2
and 1.4 Hz, 1H), 7.05 (d, J = 6.9 Hz, 1H), 7.16 (m, 4H), 7.53 (t, J = 7.6 Hz, 2H),
7.61 (t, J = 7.6 Hz, 1H), 7.85 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz, (CDCl3)) d
ppm: 19.3, 35.4, 126.5, 127.4, 127.6, 129.2, 129.6, 130.6, 131.5, 133.3, 134.6,
136.3, 140.6, 145.1. LRMS [ESI-MS +ve] calcd for (C16H16O2S+Na): 295.1,
observed: 295.0. Calcd mass for (C16H16O2S+Na): 295.1, observed: 295.0.
(E)-1-Chloro-2-(3-(phenylsulfonyl)allyl)benzene (6). 1H NMR (500 MHz,
CDCl3) d ppm: 3.63 (dd, J = 6.3 and 1.4 Hz, 2H), 6.23 (tt, J = 15.0 and 1.4 Hz,
1H), 7.13 (dt, J = 15.0 and 6.3 Hz, 1H), 7.17 (m, 1H), 7.22 (m, 2H) 7.37 (m, 1H),
7.53 (t, J = 7.7 Hz, 2H), 7.62 (t, J = 7.7 Hz, 1H), 7.86 (d, J = 7.7 Hz, 2H). 13C NMR
(100 MHz, (CDCl3)) d ppm: 35.4, 127.3, 127.6, 128.8, 129.3, 129.9, 130.8, 131.9,
133.3, 134.1, 134.3, 140.4, 143.7. LRMS [ESI-MS +ve] calcd for
(C15H13ClO2S+Na): 315.0, observed: 315.0.
Acknowledgments
We thank the Professional Staff Congress of the City University
of New York for financial support of this work. We also wish to
thank Professor Sasan Karimi for his valuable discussion during
the preparation of this manuscript.
(E)-1-Methyl-4-(3-(phenylsulfonyl)allyl)benzene (7). 1H NMR (400 MHz,
CDCl3) d ppm: 2.32 (s, 3H), 3.51 (dd, J = 6.6 and 1.8 Hz, 2H), 6.25 (dt, J = 15.0
and 1.8 Hz, 1H), 7.00 (d, J = 8.0 Hz, 2H) 7.11 (d, J = 8.0 Hz, 2H), 7.13 (dt, J = 15.0
and 6.6 Hz, 1H), 7.52 (tt, J = 7.6 and 1.4 Hz, 2H), 7.61 (tt, 7.6 and 1.4 Hz, 1H),
7.86 (dd, J = 7.6 and 1.4 Hz, 2H). 13C NMR (100 MHz, (CDCl3)) d ppm: 21.0, 37.2,
127.6, 128.7, 129.3, 129.6, 131.3, 133.1, 133.3, 136.7, 140.6, 145.8. LRMS [ESI-
MS +ve] calcd for (C16H16O2S+Na): 295.1, observed: 295.0.
Supplementary data
Supplementary data (1H, 13C, and 2D NMR spectra and details of
the X-ray structure determination) associated with this article can
be found, in the online version, at http://dx.doi.org/10.1016/
j.tetlet.2013.03.056.
(E)-1-Methoxy-4-(3-(phenylsulfonyl)allyl)benzene (8). 1H NMR (400 MHz,
CDCl3) d ppm: 3.50 (dd, J = 6.6 and 1.3 Hz, 2H), 3.79 (s, 3H), 6.23 (dt, J = 14.9
and 1.3 Hz, 1H), 6.84 (d, J = 8.6 Hz, 2H), 7.03 (d, J = 8.6 Hz, 2H), 7.13 (dt, J = 14.9
and 6.6 Hz, 1H), 7.53 (tt, J = 7.6 and 1.3 Hz, 2H), 7.61, (tt, 7.6 and 1.3 Hz, 1H),

D. Dana et al. / Tetrahedron Letters 54 (2013) 2717–2721
2721
7.86 (dd, J = 7.6 and 1.3 Hz, 2H). 13C NMR (100 MHz, (CDCl3)) d ppm: 36.8, 55.3,
114.3, 127.6, 128.1, 129.3, 129.9, 131.2, 133.3, 140.6, 145.9, 158.7. LRMS [ESI-
MS +ve] calcd for (C16H16O3S+Na): 311.1, observed: 311.0.
27. Bu, X. L.; Hong, L. C.; Liu, R. T.; Hong, J. Q.; Zhang, Z. X.; Zhou, X. G. Tetrahedron
2012, 68, 7960.
28. Castro, L. C. M.; Li, H. Q.; Sortais, J. B.; Darcel, C. Chem. Commun. 2012, 10514.
29. Kavanagh, S. A.; Piccinini, A.; Fleming, E. M.; Connon, S. J. Org. Biomol. Chem.
2008, 6, 1339.
30. Roberts, J. C.; Pincock, J. A. Can. J. Chem. 2003, 81, 709.
31. Chen, G. Q.; Xu, Z. J.; Zhou, C. Y.; Che, C. M. Chem. Commun. (Camb.) 2011,
10963.
32. All calculations were carried out in vacuum using SPARTAN program (Spartan ‘10,
version 1.1.0, Wavefunction Inc., Irvine, CA, 2011). The structures of the E and Z
isomers of 2, 9, 16, and 19 were minimized using MM2 calculations. The
minimized structures were then further subjected to DFT calculations using
B3LYP/6-311G⁄ basis set to obtain the equilibrium geometries and total
energies. From the energy-minimized structures of 2 and 16, one of the
methylene protons was removed to create the anion.
(Cinnamylsulfonyl)benzene (9). [see Table 1for 1H and 13C NMR assignments].
LRMS [ESI-MS +ve] calcd for (C15H14O2S+Na): 281.1, observed: 281.2.
(E)-4-(3-(Phenylsulfonyl)prop-1-en-1-yl)-1,10-biphenyl
(10).
1H
NMR
(500 MHz, (CD3)2CO) d ppm: 4.12 (d, J = 7.6 Hz, 2H), 6.22 (m, 1H), 6.53 (d,
J = 15.9 Hz, 1H), 7.32–7.51 (m, 5H), 7.59–7.77 (m, 7H), 7.92 (d, J = 7.4 Hz, 2H).
13C NMR (125 MHz, (CD3)2CO) d ppm: 59.66, 116.24, 126.69, 127.09, 127.10,
127.51, 128.37, 128.90, 129.14, 133.67, 135.32, 137.96, 139.30, 140.24, 140.77.
LRMS [ESI-MS +ve] calcd for (C21H18O2S+Na): 357.1, observed: 357.2.
(E)-1-(3-(Phenylsulfonyl)prop-1-en-1-yl)naphthalene (11). 1H NMR (400 MHz,
(CDCl3) d ppm: 4.09 (dd, J = 7.65, 1.0 Hz, 2H), 6.13 (m, 1H), 7.08 (d, J = 15.6 Hz,
1H), 7.38–7.96 (m, 12H). 13C NMR (100 MHz, (CDCl3)) d ppm: 60.69, 118.51,
123.50, 124.30, 125.57, 125.99, 126.26, 128.56, 128.68, 128.86, 129.21, 130.84,
133.46, 133.53, 133.80, 136.98, 138.28. LRMS [ESI-MS +ve] calcd for
(C19H16O2S+Na): 331.1, observed: 331.2.
33. Ohlinger, W. S.; Klunzinger, P. E.; Deppmeier, B. J.; Hehre, W. J. J. Phys. Chem. A
2009, 113, 2165.
34. Lee, P. S.; Du, W.; Boger, D. L.; Jorgensen, W. L. J. Org. Chem. 2004, 69, 5448.
35. Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87.
(E)-1-Methyl-2-(3-(phenylsulfonyl)prop-1-en-1-yl)benzene (12). 1H NMR
(500 MHz, (CDCl3)) d ppm: 2.13 (s, 3H), 3.98 (d, J = 7.6 Hz, 2H), 5.98 (dt,
J = 15.5, 7.6 Hz, 1H), 6.56 (d, J = 15.5 Hz, 1H), 7.10 (dd, J = 7.4, 2.0 Hz, 1H), 7.16
(td, J = 7.4, 2.0 Hz, 1H), 7.19 (td, J = 7.4, 2.0 Hz, 1H), 7.34 (dd, J = 7.4, 2.0 Hz, 1H),
7.54 (tt, J = 7.5, 1.3 Hz, 2H), 7.64 (tt, J = 7.5, 1.3 Hz, 1H), 7.90 (dd, J = 7.5, 1.3 Hz,
2H). 13C NMR (100 MHz, (CDCl3)) d ppm: 19.5, 60.7, 116.6, 125.9, 126.2, 128.4,
128.6, 129.1, 130.3, 133.8, 134.9, 135.6, 137.3, 138.4. LRMS [ESI-MS +ve] calcd
for (C16H16O2S+Na): 295.1, observed: 295.0.
36. Havens, S. J.; Hergenrother, P. M. J. Org. Chem. 1985, 50, 1763.
37. Lerebours, R.; Wolf, C. Org. Lett. 2007, 9, 2737.
38. (3-(Phenylsulfonyl)prop-1-ene-1,1-diyl)dibenzene (24) 1H NMR (500 MHz,
CDCl3)
d ppm: 3.93 (d, J = 7.9 Hz, 2H), 6.15 (t, J = 7.9 Hz, 1H), 6.67 (d,
J = 7.6 Hz, 2H), 7.16 (m, 2H), 7.23 (t, J = 7.6 Hz, 2H), 7.27 (m, 4H), 7.51 (t,
J = 7.6 Hz, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.80 (d, J = 7.6 Hz, 2H). 13C NMR
(100 MHz, CDCl3) d ppm: 57.5, 114.0, 127.4, 127.8, 128.2, 128.3, 128.4, 128.5,
129.1, 129.2, 133.7, 137.7, 138.5, 140.7, 149.7. LRMS [ESI-MS +ve] calcd for
(C21H18O2S+Na): 357.1, observed: 357.1.
(E)-1-Chloro-2-(3-(phenylsulfonyl)prop-1-en-1-yl)benzene (13). 1H NMR
(400 MHz, (CDCl3)) d ppm: 4.00 (d, J = 7.6 Hz, 2H), 6.12 (tt, J = 15.7, 7.6 Hz,
1H), 6.71 (d, J = 15.7 Hz, 1H), 7.21 (m, 2H), 7.31 (m, 1H), 7.46 (m, 1H), 7.55 (tt,
39. Yamamoto, Y.; Nisimura, T.; Nozaki, H. Bull. Chem. Soc. Jpn. 1971, 44, 541.
40. Farrugia, L. J. J. Appl. Crystallogr. 1997, 30, 565.
J = 7.4, 1.4 Hz, 2H), 7.65 (tt, J = 7.4, 1.4 Hz, 1H), 7.89 (dd, J = 7.4, 1.4 Hz, 2H). 13
C
NMR (100 MHz, CDCl3) d ppm: 60.5, 118.2, 127.0, 127.1, 128.5, 129.2, 129.5,
129.7, 133.2, 133.8, 133.9, 135.4, 138.2. LRMS [ESI-MS +ve] calcd for
(C15H13ClO2S+Na): 315.0, observed: 315.0.
41. (E)-(Pent-1-en-1-ylsulfonyl)benzene (16E). 1H NMR (500 MHz, CDCl3) d ppm:
0.92 (m, 3H), 1.50 (m, 2H), 2.23 (m, 2H), 6.33 (d, J = 15.0 Hz, 1H), 7.00 (m, 1H),
7.54 (m, 3H), 7.87 (m, 2H). 13C NMR (125 MHz, CDCl3) d ppm: 13.6, 20.9, 33.4,
127.5, 129.3, 130.4, 133.3, 140.7, 147.1. LRMS [ESI-MS +ve] calcd for
(C11H14O2S+Na): 233.1, observed: 233 (Z)-(pent-1-en-1-ylsulfonyl)benzene
(16Z). 1H NMR (500 MHz, CDCl3) d ppm: 0.92 (m, 3H), 1.50 (m, 2H), 2.64 (m,
2H), 6.33 (m, 2H), 7.54 (m, 3H), 7.92 (m, 2H). 13C NMR (125 MHz, CDCl3) d
ppm: 13.7, 21.9, 29.6, 127.2, 129.3, 130.5, 133.4, 141.8, 147.5. LRMS [ESI-MS
+ve] calcd for (C11H14O2S+Na): 233.1, observed: 233.2.
(E)-1-Methyl-4-(3-(phenylsulfonyl)prop-1-en-1-yl)benzene (14). 1H NMR
(400 MHz, CDCl3)
d ppm: 2.34 (s, 3H), 3.94 (d, J = 7.6 Hz, 2H), 6.05 (dt,
J = 15.6 and 7.6 Hz, 1H), 6.32 (d, J = 15.6 Hz and 1H) 7.11 (d, J = 8.0 Hz, 2H), 7.18
(d, J = 8.0 Hz, 2H), 7.53 (tt, J = 7.6 and 1.4 Hz, 2H), 7.63 (tt, 7.6 and 1.4 Hz, 1H),
7.88 (dd, J = 7.6 and 1.4 Hz, 2H). 13C NMR (100 MHz, (CDCl3)) d ppm: 21.3, 60.6,
114.0, 126.6, 128.6, 129.1, 129.4, 133.0, 133.7, 138.4, 138.6, 139.2. Calcd mass
for (C16H16O2S+Na): 295.1, observed: 295.0.
(E)-(Pent-2-en-1-ylsulfonyl)benzene (19E). 1H NMR (500 MHz, CD3OD) d ppm:
0.88 (t, J = 7.52 Hz, 3H), 1.98 (m, 2H), 3.87 (d, J = 7.31 Hz, 2H), 5.37(m, 1H),
5.56 (m, 1H), 7.71 (m, 2H), 7.71 (m, 1H), 7.86 (m, 2H). 13C NMR (125 MHz,
MeOD-D4) d ppm: 12.0, 25.2, 59.1, 115.2, 128.3, 128.8, 133.5, 138.3, 142.8.
LRMS [ESI-MS +ve] calcd for (C11H14O2S+Na): 233.1, observed: 233.2.
(Z)-(Pent-2-en-1-ylsulfonyl)benzene (19Z). 1H NMR (500 MHz, CD3OD) d ppm:
0.71 (t, J = 7.55 Hz, 3H), 1.77 (m, 2H), 3.98 (d, J = 8.01, 2H), 5.37 (m, 1H), 5.70
(m, 1H), 7.62 (m, 2H), 7.71 (m, 1H), 7.89 (m, 2H). 13C NMR (125 MHz,
MeOD-D4) d ppm: 12.3, 20.1, 54.2, 114.5, 128.2, 128.9, 133.6, 138.6, 140.7.
LRMS [ESI-MS +ve] calcd for (C11H14O2S+Na): 233.1, observed: 233.2.
42. Haynes, R. K.; Schober, P. A.; Binns, M. R. Aust. J. Chem. 1987, 40, 1223.
43. Wnuk, S. F.; Garcia, P. I.; Wang, Z. Z. Org. Lett. 2004, 6, 2047.
(E)-1-Methoxy-4-(3-(phenylsulfonyl)prop-1-en-1-yl)benzene (15). 1H NMR
(500 MHz, CDCl3)
d ppm: 3.81 (s, 3H), 3.93 (d, J = 7.7 Hz, 2H), 5.96 (tt,
J = 15.6, 7.7 Hz, 1H), 6.31 (d, J = 15.6 Hz, 1H), 6.84 (dd, J = 8.7 Hz, 2H), 7.23 (d,
J = 8.7 Hz, 2H), 7.54 (t, J = 7.7 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H), 7.88 (d, J = 7.7 Hz,
2H). 13C NMR (100 MHz, CDCl3) d ppm: 55.3, 60.6, 112.6, 114.1, 127.9, 128.5,
128.6, 129.1, 133.7, 138.5, 138.7, 159.9. LRMS [ESI-MS +ve] calcd for
(C16H16O3S+Na): 311.1, observed: 311.0.
23. Michrowska, A.; Bieniek, M.; Kim, M.; Klajn, R.; Grela, K. Tetrahedron 2003, 59,
4525.
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25. Cambridge Crystallographic Data Centre deposition No. 916842. The data can
be obtained free from Cambridge Crystallographic Data Centre via http://
www.ccdc.cam.ac.uk/data_request/cif.
44. Gais, H. J.; Babu, G. S.; Gunter, M.; Das, P. Eur. J. Org. Chem. 2004, 1464.
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