Highly regio- and stereoselective synthesis of β-phenyl-chalcogenyl allyl sulfones by hydrochalcogenation reaction of 1,2-allenyl sulfones

Article abstract of DOI:10.1080/00397910600764212

The hydrochalcogenation of allenyl sulfones with sodium organyl chalcogenolates can proceed smoothly to give β-phenylchalcogenyl allyl sulfones in high yields with exclusive regioselectivity. For the asymmetric allenyl sulfone, the reaction has both high

Full text of DOI:10.1080/00397910600764212

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Highly Regio‐ and Stereoselective Synthesis
of β‐Phenyl‐chalcogenyl Allyl Sulfones by
Hydrochalcogenation Reaction of 1,2‐Allenyl
Sulfones
Feng Sha a , Zhimeng Wu a & Xian Huang a b
a Department of Chemistry , Zhejiang University (Campus Xixi) , Hangzhou,
China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry , Chinese Academy of Sciences , Shanghai, China
Published online: 16 Feb 2007.
To cite this article: Feng Sha , Zhimeng Wu & Xian Huang (2006) Highly Regio‐ and Stereoselective Synthesis
of β‐Phenyl‐chalcogenyl Allyl Sulfones by Hydrochalcogenation Reaction of 1,2‐Allenyl Sulfones, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:18,
2603-2612, DOI: 10.1080/00397910600764212
To link to this article: http://dx.doi.org/10.1080/00397910600764212
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Synthetic Communicationsw, 36: 2603–2612, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910600764212
Highly Regio- and Stereoselective Synthesis
of b-Phenyl-chalcogenyl Allyl Sulfones by
Hydrochalcogenation Reaction of
1,2-Allenyl Sulfones
Feng Sha and Zhimeng Wu
Department of Chemistry, Zhejiang University (Campus Xixi),
Hangzhou, China
Xian Huang
Department of Chemistry, Zhejiang University (Campus Xixi),
Hangzhou, China and State Key Laboratory of Organometallic
Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy
of Sciences, Shanghai, China
Abstract: The hydrochalcogenation of allenyl sulfones with sodium organyl chalco-
genolates can proceed smoothly to give b-phenylchalcogenyl allyl sulfones in high
yields with exclusive regioselectivity. For the asymmetric allenyl sulfone, the
reaction has both high regio- and stereoselectivity with the predominace of E-
isomer. Some applications of b-phenyltelluro and b-phenylselanyl allyl sulfone in
organic synthesis are also investigated.
Keywords: Allenyl sulfones, allyl sulfones, hydrochalcogenation, regioselectivity,
stereoselectivity
Allyl sulfones are important and versatile intermediates in organic synthesis,
especially in the synthesis of various functionlized compounds[1] and natural
products.[2] b-Functionalized allyl sulfones[3] are another class of compounds
Received in Japan December 19, 2005
Address correspondence to Xian Huang, Department of Chemistry, Zhejiang
University (Campus Xixi), Hangzhou 310028, China. E-mail: huangx@mail.hz.zj.cn
2603

2604
F. Sha, Z. Wu, and X. Huang
that has received great attention. Consequently, a general and convenient
procedure preparing for such compounds would be useful.
b-Organolchalcogenyl substituted allyl sulfones are interesting struc-
tures because they are a composite of an allyl sulfone and vinylic chalco-
genide subunit. Vinylic chacogenides and their synthetic application have
attracted remarkable interest during the past decades.[4] These compounds
have a pronounced ambident characters and are intermediates of great
synthetic potential. Our group[5] and others
[6– 8]
have found that electron-
deficient carbon–carbon triple bond can undergo hydrochalcogenation
reaction regio- and stereoselectively, affording an efficient method for the
synthesis of functionalized vinylic chalcogenides. Another class of
compounds attracting our interest is electron-deficient 1,2-dienes, which
have unique reactivities due to the presence of cumulated carbon–carbon
double bond.[9,10] Usually, one of them can be selectively reacted to give
vinylic products via delicate the tuning of the steric and electronic factors.
Accordingly, hydrochalcogenation of electron-deficient allenes would be
one of the most efficient and convenient ways to prepare b-organolchalco-
genyl substituted allyl compounds. As an extension of the studies on this
area,[11] herein we describe the regio-and stereoselectively hydrochalogenation
reaction of allenyl sulfones.
Initially, the reaction of 1,2-allenyl sulfones 1a with sodium phenyl-
tellurolates 2a, prepared by reduction of diphenylditelluride with sodium
borohydride at room temperature, was examined as shown in Scheme 1.
Thus, to an ethanol solution of sodium phenyltellurolates 2a was added the
1,2-allenyl sulfones 1a. Fortunately, the b-phenyltelluro allyl sulfone 3a
was formed in high yields with perfect regioselectivity.
Encouraged by the good results, we synthesized a series of allenyl
sulfones[12] to investigate the hydrochalcogenation reaction. As shown in
Table 1, the substrates can be mono- (entry 1), di- (entry 2), and trisubstituted
(entries 3,4) allenyl sulfones (Scheme 2). Having established reaction con-
ditions, various substituted allenyl sulfones were subjected to synthesize
b-phenylselanyl allyl sulfones (entries 5–8).
Scheme 1.

b-Phenyl-chalcogenyl Allyl Sulfones
2605
Table 1. Preparation of b-phenylchalcogenyl allyl sulfones
Entry
R1
R2
R3
PhY
Yields (%)a
Products
1
2
3
4
5
6
7
8
H
H
H
C6H5Te
C6H5Te
C6H5Te
C6H5Te
C6H5Se
C6H5Se
C6H5Se
C6H5Se
97
91
89
94
91
87
90
92
3a
3b
3c
3d
3e
3f
H
H
Ph
H
-(CH2)5-
CH3
H
CH3
H
H
H
H
H
Ph
H
-(CH2)5-
3g
3h
CH3
CH3
H
aIsolated yields based on the allenyl sulfones.
From the results in Table 1, we were pleased to find that these reactions
have exclusively regioselectivity, and only one regioisomer (3a–h) was
obtained. For the mono-, di-, or trisubstrituted allenyl sulfones, yields to
give the b-phenylselanyl (products 3a–h) allyl sulfones were very high.
The mechanism for the current regioselective hydrochalogenation
reaction is a nucleophilic conjugate addition of RY2 to allenyl sulfones at
the b-position to afford an allyl carbanion stabilized by the sulfone group.
Interestingly, when R1 = R2, the stereoselectivity of this reaction is due
to the steric facts. The two isomers can be separated carefully by chromato-
graphy on silica gel; the (E) isomers are predominant. The configuration of
the carbon–carbon double bond was determined by 2D H1-H1 NOESY experi-
ment of 3l which is Z-isomer (Scheme 3).
As shown in Table 2, when R1 = R2, the mixture of E- or
Z-b-phenylselanyl allyl sulfones was obtained. For the steric reason, the
E-isomers are major products. The PhSe group is opposite to the bulky
group on the double bond. The nucleophilic conjugate addition of RY2 to
allenyl sulfones to give the thermodynamically more stable product (higher
E-selectivity). As the size of the subtituent increases relatively, so does
steric hindrance to attack, and the more E-isomer was correspondingly
obtained.
Scheme 2.

2606
F. Sha, Z. Wu, and X. Huang
Scheme 3.
b-Phenylchalcogenyl allyl sulfones 3 are useful intermediates and have
many transformations in organic chemistry. We found that under the catalysis
of PdCl2/CuI, compound 3a could react with alkyne to give the b-allynyl
sulfones 4a and 4b in good yields (Scheme 4). Moreover compound 3e
reacted with RMgBr to produce the b-alkyl allyl sulfone 5 in moderate yields
under the catalysis of NiCl2(PPh3)2 (Scheme 5). Compounds 3 can also
undergo many important transformations in organic synthesis, such as 1,3-
rearrangement,[13] 1,3-dipolar cycloaddition,[14] and radical allylation.[15]
In conclusion, we have developed a highly efficient regioselective and the
nicer stereoselective hydrohalcogenation of allenyl sulfones to afford syntheti-
cally important b-phenylchalcogenyl allyl sulfones. The generality of this
methodology was illustrated using different allenyl sulfones. Preliminary
application studies have demonstrated the utility of b-phenyltelluro allyl
sulfone 3a and b-phenylselanyl allyl sulfone 3e as precursors for certain
potentially useful compounds.
EXPERIMENTAL
General
1H NMR spectra were recorded on Bruker Avance-400 (400 MHz) spec-
trometer in CDCl3 using TMS as the internal standard (chemical shifts in
parts per million, ppm, and J values in Hertz, Hz). IR spectra were run on
a Bruker vector 22 spectrometer. EIMS were determined with a HP5989B
Table 2. Preparation of E (orZ)-b-phenylselanyl allyl sulfones
Entry
9
R1
R2
R3
H
PhY
Yields (%)a
89
Products
p-ClC6H4
H
C6H5Se
3i(E); 3j(Z)
(E/Z ¼ 86/14)
3k(E); 3l(Z)
10
11
n-C4H9
H
H
H
C6H5Se
C6H5Se
85
86
(E/Z ¼ 80/20)
3m(E); 3n(Z)
(E/Z ¼ 61/39)
p-ClC6H4
CH3
aIsolated yields based on the allenyl sulfones.

b-Phenyl-chalcogenyl Allyl Sulfones
2607
Scheme 4.
mass spectrometer. Elemental analyses were performed on an EA-1110
instrument.
General Procedure for the Synthesis of 3a–h
To a solution of RYNa, prepared in situ by reduction of (RY)2 (0.3 mmol) with
sodium borohydride (0.7 mmol) in 2 mL of ethanol at room temperature under
nitrogen, allenyl sulfones (0.5 mmol) in 2 mL of EtOH were added dropwise.
After the reaction completed (3 min), the reaction was diluted with saturated
brine (10 mL) and extracted with ethyl acetate (3 ꢀ 20 mL). The organic layer
was dried over anhydrous MgSO4. After filtration and removal of the solvent
in vacuo, the residue was purified via chromatography on silica gel with
n-hexane/ethyl acetate (6:1) as the eluent to give the product 3.
Data
1
3a: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.89 (d, J ¼ 9.44 Hz, 2H), 7.74
(m, 2H), 7.65 (t, 1H), 7.55 (t, 2H), 7.35 (t, 1H), 7.24 (t, 2H), 6.04 (s, 1H),
5.60 (s, 1H), 4.13 (s, 2H); 13C NMR (100 MHz, CDCl3) d ¼ 139.7, 137.9,
133.8, 133.2, 129.5, 128.9, 128.7, 128.5, 113.9, 112.6, 67.1; IR nmax (neat):
3062, 1317, 1137, 743 cm21; MS (EI, 70 eV): m/z (%) ¼ 57 (100), 386 (1)
[Mþ]. Anal. calcd. for C15H14O2STe: C, 46.68; H, 3.66; found: C, 46.61;
H, 3.72.
3b: Solid, mp 134–136 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.63
(d, J ¼ 7.80 Hz, 2H), 7.59 (m, 3H), 7.37 (m, 4H), 7.14 (m, 6H), 7.03
Scheme 5.

2608
F. Sha, Z. Wu, and X. Huang
(s, 1H), 6.04 (s, 1H), 4.91 (s, 1H); 13C NMR (100 MHz, CDCl3) d ¼ 139.6,
138.2, 133.4, 131.1, 130.6, 130.3, 129.5, 128.9, 128.8, 128.6, 128.5, 128.3,
118.3, 113.7, 78.1; IR nmax (neat): 3061, 1314, 1146, 787 cm21; MS (EI,
70 eV): m/z (%) ¼ 115 (100), 462 (5) [Mþ]. Anal. calcd. for C21H18O2STe:
C, 54.59; H, 3.93; found: C, 54.64; H, 3.98.
1
3c: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.84 (m, 3H), 7.60 (m, 2H), 7.52
(m, 5H), 4.50 (s, 2H), 2.45 (m, 2H), 2.23 (m, 2H), 1.44 (m, 6H); 13C NMR
(100 MHz, CDCl3) d ¼ 159.4, 138.7, 136.7, 133.4, 128.9, 128.8, 128.7, 127.1,
126.9, 115.4, 95.3, 63.9, 41.7, 26.1, 25.6, 23.7; IR nmax (neat): 2930, 1306,
1142, 731 cm21; MS (EI, 70 eV): m/z (%) ¼ 101 (100), 454 (17) [Mþ]. Anal.
calcd. for C20H22O2STe: C, 52.90; H, 4.88; found: C, 52.84; H, 4.97.
3d: Solid, mp 70–72 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.81 (m, 2H), 7.57
(m, 5H), 7.24 (m, 1H), 7.19 (m, 2H), 4.40 (s, 2H), 2.01 (s, 3H), 1.76 (s, 3H);
13C NMR (100 MHz, CDCl3) d ¼ 152.4, 139.1, 137.4, 133.7, 129.4, 129.0,
128.7, 127.6, 115.2, 98.1, 64.7, 31.3, 20.6; IR nmax (neat): 3060, 1306,
1138, 740 cm21; MS (EI, 70 eV): m/z (%) ¼ 77 (100), 414 (13) [Mþ].
Anal. calcd. for C17H18O2STe: C, 49.32; H, 4.38; found: C, 49.44; H, 4.37.
1
3e: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.88 (m, 2H), 7.60 (m, 3H), 7.40
(m, 2H), 7.30 (m, 3H), 5.71 (s, 1H), 5.40 (s, 1H), 3.99 (s, 2H); 13C NMR
(100 MHz, CDCl3): d ¼ 138.1, 134.9, 133.9, 129.5, 129.1, 129.0, 128.8,
128.7, 128.6, 125.5, 63.5; IR nmax (neat): 3059, 1318, 1146, 688 cm21; MS
(EI, 70 eV): m/z (%) ¼ 77 (100), 338 (15) [Mþ]. Anal. calcd. for
C15H14O2SSe: C, 53.41; H, 4.18; found: C, 53.48; H, 4.12.
1
3f: Solid, mp 151–152 8C. H NMR (400 MHz, CDCl3): d ¼ 7.56 (m, 3H),
7.38 (m, 2H), 7.32 (m, 4H), 7.23 (m, 6H), 6.70 (s, 1H), 5.82 (s, 1H), 4.76
(s, 1H); 13C NMR (100 MHz, CDCl3): d ¼ 138.0, 134.5, 133.4, 132.7,
130.5, 130.1, 129.4, 128.9, 128.9, 128.6, 128.3, 128.2, 128.1, 124.0, 75.2;
IR nmax (neat): 3060, 1318, 1147, 754 cm21; MS (EI, 70 eV): m/z
(%) ¼ 84 (100), 414 (3) [Mþ]. Anal. calcd. for C21H18O2SSe: C, 61.01;
H, 4.39; found: C, 61.09; H, 4.33.
1
3g: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.83 (m, 3H), 7.60 (m, 1H), 7.49
(m, 3H), 7.17 (m, 3H), 4.23 (s, 2H), 3.53 (m, 2H), 2.26 (m, 2H), 1.50
(m, 6H); 13C NMR (100 MHz, CDCl3): d ¼ 157.9, 139.1, 133.6, 130.9,
129.1, 128.9, 128.6, 127.2, 126.5, 108.4, 61.5, 36.3, 32.1, 27.8, 27.6, 25.9;
IR nmax (neat): 2930, 1131, 1142, 737 cm21; MS (EI, 70 eV): m/z
(%) ¼ 107 (100), 406 (10) [Mþ]. Anal. calcd. for C20H22O2SSe: C, 59.25;
H, 5.47; found: C, 59.33; H, 5.50.
3h: Solid, mp 88–90 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.80
(d, J ¼ 7.84 Hz, 2H), 7.61 (m, 1H), 7.50 (m, 2H), 7.18 (m, 5H), 4.18

b-Phenyl-chalcogenyl Allyl Sulfones
2609
(s, 2H), 2.02 (s, 3H), 1.81 (s, 3H); 13C NMR (100 MHz, CDCl3): d ¼ 150.3,
139.2, 133.7, 131.3, 130.8, 129.2, 129.0, 128.6, 126.8, 111.4, 62.0, 26.4, 21.8;
IR nmax (neat): 2914, 1307, 1139, 743 cm21; MS (EI, 70 eV): m/z (%) ¼ 183
(100), 366 (18) [Mþ]. Anal. calcd. for C17H18O2SSe: C, 55.89; H, 4.97; found:
C, 55.94; H, 5.01.
3i: Solid, mp 76–78 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.83
(d, J ¼ 9.32 Hz, 2H), 7.63 (t, 1H), 7.49 (t, 2H), 7.44 (m, 2H), 7.26 (m, 5H),
7.08 (d, J ¼ 8.36 Hz, 2H), 6.99 (s, 1H), 4.26 (s, 2H); 13C NMR (100 MHz,
CDCl3): d ¼ 139.8, 139.1, 134.4, 133.9, 133.8, 133.7, 129.4, 129.3, 129.2,
129.0, 128.6, 128.4, 128.3, 122.8, 59.7; IR nmax (neat): 3061, 1316, 1140,
742 cm21; MS (EI, 70 eV): m/z (%) ¼ 115 (100), 448 (14) [Mþ]. Anal.
calcd. for C21H17ClO2SSe: C, 56.32; H, 3.83; found: C, 56.24; H, 3.91.
3j: Solid, mp 107–109 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.83
(d, J ¼ 8.40 Hz, 2H), 7.67 (t, 1H), 7.55 (t, 2H), 7.30 (m, 9H), 6.97 (s, 1H),
3.97 (s, 2H); 13C NMR (100 MHz, CDCl3): d ¼ 140.3, 138.7, 134.5, 133.7,
133.6, 133.4, 130.1, 129.4, 129.3, 129.0, 128.7, 128.5, 128.4, 121.9, 55.7;
IR nmax (neat): 3060, 1314, 1138, 744 cm21; MS (EI, 70 eV): m/z
(%) ¼ 115 (100), 448 (19) [Mþ]. Anal. calcd. for C21H17ClO2SSe:
C, 56.32; H, 3.83; found: C, 56.27; H, 3.93.
3k: Solid, mp 67–69 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.87
(d, J ¼ 7.40 Hz, 2H), 7.66 (t, 1H), 7.54 (t, 2H), 7.31 (m, 2H), 7.25 (m, 3H),
6.28 (t, 1H), 4.08 (s, 2H), 1.99 (m, 2H), 1.27 (m, 4H), 0.91 (t, 3H); 13C NMR
(100 MHz, CDCl3): d ¼ 147.7, 138.9, 133.8, 132.8, 129.7, 129.2, 129.0,
128.7, 127.5, 116.5, 59.6, 30.7, 30.1, 22.2, 13.8; IR nmax (neat): 2955, 1309,
1148, 746 cm21; MS (EI, 70 eV): m/z (%) ¼ 252 (100), 394 (11) [Mþ].
Anal. calcd. for C19H22O2SSe: C, 58.01; H, 5.64; found: C, 58.11; H, 5.56.
3l: Solid, mp 73–75 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.87
(d, J ¼ 7.41 Hz, 2H), 7.65 (t, 1H), 7.53 (t, 2H), 7.27 (m, 5H), 6.07 (t, 1H),
3.93 (s, 2H), 2.27 (m, 2H), 1.30 (m, 4H), 0.89 (t, 3H); 13C NMR (100 MHz,
CDCl3): d ¼ 146.1, 138.5, 133.7, 132.8, 129.3, 129.1, 128.9, 128.8, 127.5,
118.4, 64.0, 32.2, 30.8, 22.2, 13.8; IR nmax (neat): 2961, 1307, 1141,
741 cm21; MS (EI, 70 eV): m/z (%) ¼ 95 (100), 394 (11) [Mþ]. Anal.
calcd. for C19H22O2SSe: C, 58.01; H, 5.64; found: C, 58.07; H, 5.49.
3m: Solid, mp 96–98 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.68
(d, J ¼ 7.32 Hz, 2H), 7.63 (t, 1H), 7.47 (t, 2H), 7.35 (m, 2H), 7.26 (m, 5H),
6.94 (d, J ¼ 8.40 Hz, 2H), 4.10 (s, 2H), 2.25 (s, 3H); 13C NMR (100 MHz,
CDCl3): d ¼ 151.5, 139.8, 139.6, 133.5, 133.4, 132.0, 130.3, 129.4, 129.0,
128.9, 128.7, 128.5, 127.3, 116.6, 62.0, 27.1; IR nmax (neat): 3060, 2920,
1312, 1141, 739 cm21; MS (EI, 70 eV): m/z (%) ¼ 129 (100), 462 (29) [Mþ].
Anal. calcd. for C22H19ClO2SSe: C, 57.21; H, 4.15; found: C, 57.29; H, 4.08.

2610
F. Sha, Z. Wu, and X. Huang
3n: Solid, mp 120–122 8C. 1H NMR (400 MHz, CDCl3): d ¼ 7.91
(d, J ¼ 6.80 Hz, 2H), 7.67 (t, 1H), 7.60 (t, 2H), 7.24 (m, 7H), 7.02
(d, J ¼ 8.41 Hz, 2H), 4.18 (s, 2H), 2.06 (s, 3H); 13C NMR (100 MHz, CDCl3):
d ¼ 149.2, 142.6, 139.6, 134.2, 134.0, 133.8, 130.0, 129.6, 129.4, 129.1,
129.0, 128.8, 128.1, 116.6, 60.6, 23.5; IR nmax (neat): 3061, 2923, 1315, 1141,
738 cm21; MS (EI, 70 eV): m/z (1%) ¼ 321 (100), 462 (33) [Mþ]. Anal.
calcd. for C22H19ClO2SSe: C, 57.21; H, 4.15; found: C, 57.17; H, 4.12.
Preparation of b-Alkynyl Allyl Sulfone 4
The mixture of 3a (0.386 g, 1 mmol), terminal acetylene (2.0 mmol), PdCl2
(10 mol%), CuI (10 mol%), and Et3N (1.0 mmol) in 2 mL of MeCN was
stirred at room temperature for about 24 h under N2. After the reaction
completed, the reaction was diluted with saturated brine (10 mL) and
extracted with ethyl acetate (3 ꢀ 15 mL). The organic layer was dried over
anhydrous MgSO4. After filtration and removal of the solvent in vacuo, the
residue was purified via chromatography on silica gel with n-hexane/ethyl
acetate (3:1) as the eluent to give the products.
Data
1
4a: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.93 (m, 2H), 7.57 (m, 3H), 5.66
(s, 1H), 5.44 (s, 1H), 4.00 (s, 2H), 3.89 (s, 2H), 3.29 (s, 3H); 13C NMR
(100 MHz, CDCl3) d ¼ 138.1, 133.7, 130.3, 128.8, 128.7, 118.7, 86.5, 84.4,
62.7, 59.7, 57.4; IR nmax (neat): 2929, 2361, 1733, 1313, 1150 cm21; MS
(EI, 70 eV): m/z (%) ¼ 77 (100), 125 (83), 250 (3) [Mþ]. Anal. calcd. for
C13H14O3S: C, 62.38; H, 5.64. found: C, 62.45, H, 5.57.
1
4b: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.92 (t, 2H), 7.64 (m, 1H), 7.54
(t, 2H), 5.52 (s, 1H), 5.35 (s, 1H), 3.87 (s, 2H), 2.07 (t, 2H), 1.32 (m, 4H),
0.89 (t, 3H); 13C NMR (100 MHz, CDCl3) d ¼ 138.3, 133.6, 128.7, 128.6,
128.2, 119.7, 92.2, 78.9, 63.2, 30.2, 21.7, 18.6, 13.4; IR nmax (neat): 3004,
2343, 1729, 1161 cm21; MS (EI, 70 eV): m/z (%) ¼ 77 (100), 109 (47),
262 (2) [Mþ]. Anal. calcd. for C15H18O2S: C, 68.67; H, 6.92. found:
C, 68.73, H, 6.85.
Preparation of b-Aryl Allyl Sulfone 5
Grignard reagent (5 mmol) in 10 ml of THF was added dropwise to a mixture
of 3e (0.338 g, 1 mmol) and NiCl2(PPh3)2 (0.020 mg, 3 mol%) in 5 mL of dry
THF, and the mixture was stirred at room temperature for about 27 h under N2.
After the reaction completed, it was followed by protolysis with saturated

b-Phenyl-chalcogenyl Allyl Sulfones
2611
aqueous NH4Cl (5 mL) and then extracted with diethyl ether (3 ꢀ 15 mL).
The organic layer was dried over anhydrous MgSO4. After filtration and
removal of the solvent in vacuo, the residue was purified via chromatography
on silica gel with n-hexane/ethyl acetate (7:1) as the eluent to give the
products.
Data
1
5: Oil, H NMR (400 MHz, CDCl3): d ¼ 7.92 (m, 2H), 7.68 (t, 1H), 7.58
(t, 2H), 7.32 (m, 3H), 7.26 (m, 2H), 5.42 (s, 1H), 5.19 (s, 1H), 3.91 (s, 2H);
13C NMR (100 MHz, CDCl3): d ¼ 138.2, 133.9, 133.4, 133.2, 131.3, 129.4,
129.1, 128.9, 128.6, 121.3, 61.9; MS (EI, 70 eV): m/z (%) ¼ 77 (100), 258
(22) [Mþ]. Anal. calcd. for C15H14O2S: C, 69.74; H, 5.46. found: C, 69.68,
H, 5.55
ACKNOWLEDGMENT
We are grateful to the National Natural Science Foundation of China (Project
No. 20272050, 20332060) for financial support.
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