Enantioselective oxysulfenylation and oxyselenenylation of olefins catalyzed by chiral Br?nsted acids

Article abstract of DOI:10.1016/j.tet.2012.01.006

This paper describes Br?nsted acid catalyzed enantioselective oxysulfenylation and oxyselenenylation of olefins. Enantiomerically enriched tetrahydrofurans are formed with up to 63% ee with dibenzoyl-d-tartaric acid and its derivatives as catalyst. Chiral

Full text of DOI:10.1016/j.tet.2012.01.006

Tetrahedron 68 (2012) 2728e2735
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Enantioselective oxysulfenylation and oxyselenenylation of olefins catalyzed
by chiral Brønsted acids
,b,
Huan Guan a, Haining Wang a, Deshun Huang a, Yian Shi a
*
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100190, China
b Department of Chemistry, Colorado State University, Fort Collins, CO 80523, United States
a r t i c l e i n f o
a b s t r a c t
Article history:
This paper describes Brønsted acid catalyzed enantioselective oxysulfenylation and oxyselenenylation of
Received 23 October 2011
Received in revised form 4 January 2012
Accepted 4 January 2012
olefins. Enantiomerically enriched tetrahydrofurans are formed with up to 63% ee with dibenzoyl-
D-
tartaric acid and its derivatives as catalyst. Chiral -carboxyl sulfides and selenides have also been ob-
b
tained with up to 50% and 84% ee, respectively, via enantioselective desymmetrization of thiiranium and
seleniranium ions in the presence of catalytic amounts of chiral binaphthol derived N-triflyl
phosphoramide.
Available online 26 January 2012
Keywords:
Sulfenylation
Ó 2012 Elsevier Ltd. All rights reserved.
Selenenylation
Thiiranium ions
Seleniranium ions
Desymmetrization
Enantioselective
1. Introduction
efforts on chiral Brønsted acid catalyzed asymmetric sulfenylation
and selenenylation of olefins.
Electrophilic sulfur and selenium additions to olefins provide
important methods to introduce functional groups onto CeC dou-
ble bonds.1 Development of asymmetric processes for these
transformations is highly desirable. Significant progress has been
made in asymmetric sulfenylation and selenenylation using chiral
sulfur2 or selenium1bed,2,3 reagents. Very recently, catalytic asym-
metric systems with chiral Lewis bases have also been developed.4
As a part of our general interest in the area of oxidation of olefins to
introduce various heteroatoms such as O, N, Cl, Br, I, S (Scheme 1),5
we have been investigating acid catalyzed electrophilic sulfur and
selenium additions to olefins.5c,d,6e12 Herein we wish to report our
2. Results and discussion
The reactivity of several sulfenamides and benzenesulfenates
was initially examined using cis-4-decen-1-ol (1a) as substrate and
CSA as catalyst. While N-(phenylthio)succinimide (2a)13 showed
a low reactivity for the sulfetherification (Table 1, entry 1), both 1-
phenylsulfanyl[1,2,4]triazole (2b)14 and methyl benzenesulfenate
(2c)6b,15 were found to be highly reactive, giving product 4a in 81%
and 86% yields in 4 h (entries 2 and 3). Trifluoroethyl benzene-
sulfenate (2d)16 displayed even higher reactivity, giving the cycli-
zation product in 98% yield in only 1 h (Table 1, entry 4). Further
studies showed that weaker acids such as HOAc, PhCOOH, and
(PhO)2POOH could also catalyze the sulfetherification (Table 1,
entries 5e7).
Several chiral Brønsted acid catalysts 3ae3h were subsequently
tested for the sulfetherification. As shown in Table 2, chiral phos-
phoric acids 3a1 and 3a2,17,18 trifluoromethanesulfonamide 3c,19
and N-acetylproline (3d) gave only trace amounts of the product
(entries 1, 2, 5, and 6). Good yields but little ee’s were obtained with
chiral phosphoric acid 3a3 and N-triflyl phosphoramide 3b20 (en-
Scheme 1.
tries 3 and 4). (ꢀ)-
D
-Dibenzoyltartaric acid (3e) gave the product 4a
* Corresponding author. Fax: þ1 970 4911801; e-mail address: yian@lamar.
colostate.ed (Y. Shi).
in 88% yield and 55% ee (entry 7). Slightly higher ee (61% ee) was
0040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2012.01.006

H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
2729
Table 1
obtained with monoester 3h (entry 13). It was somewhat un-
expected that ee’s were decreased with stoichiometric amounts of
the acids (entry 7 vs 8, entry 9 vs 10).
Initial screening of sulfur reagentsa
Various substrates were treated with trifluoroethyl benzene-
sulfenate (2d) and chiral acid 3h. The results are summarized in
Table 3. In all these cases, the cyclization proceeded regiose-
lectively, giving tetrahydrofurans in 68e90% yield and 31e63% ee.
Little product or messy mixture was obtained for trans-alkenols
under the current reaction conditions.
Entry
PhSX
Acid (3)
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
2a
2b
2c
2d
2d
2d
2d
(ꢂ)CSA
4
4
4
1
4
4
4
NRc
81
86
98
90
74
65
Table 3
(ꢂ)CSA
Enantioselective sulfetherification of alkenolsa
(ꢂ)CSA
(ꢂ)CSA
HOAc
PhCOOH
(PhO)2POOH
a
Entry
Substrate
Yieldc (%)
eed,e (%)
Reactions were carried out with 1a (0.50 mmol),
2
(0.75 mmol), and 3
(0.10 mmol) in CHCl3 (5.0 mL) at 25 ꢁC.
1
2
R¼nC5H11, 1a
89
72
90
74
68
76
61
51
53
31
50
63
b
Isolated yield.
No reaction.
R¼Me, 1b
c
3
R¼Et, 1c
4b
5
R¼tBu, 1d
Table 2
R¼CH2Bn, 1e
Screening of chiral acidsa
6
R¼nC9H19, 1f
7
84
44
a
Reactions were carried out with
1 (0.50 mmol), 2d (0.60 mmol), and 3h
(0.05 mmol) in CHCl3 (5.0 mL) and toluene (2.5 mL) at ꢀ85 ꢁC for 48 h.
b
Reaction was carried out with
1 (0.50 mmol), 2d (0.60 mmol), and 3h
(0.10 mmol) in CHCl3 (5.0 mL) at ꢀ60 ꢁC for 48 h.
c
Isolated yield.
Determined by chiral HPLC (Chiralcel OD-H column).
The stereochemistry indicated is relative stereochemistry.
d
e
To further explore the reaction mechanism, benzenesulfenate 5
was prepared and subjected to the reaction conditions. Only race-
mic product 4a was obtained (Scheme 2), suggesting that the
sulfenate is unlikely to be involved during the cyclization. A precise
understanding of the reaction mechanism awaits further studies.
Scheme 2.
Entry
3 (mol %)
Time (h)
Yieldb (%)
eec,d (%)
1
2
3
4
5
6
7
8
3a1 (20%)
3a2 (10%)
3a3 (10%)
3b (10%)
3c (10%)
3d (20%)
3e (10%)
3e (100%)
3f (20%)
3f (100%)
3g (20%)
3h (20%)
3h (10%)
d
24
24
24
24
24
24
24
24
24
24
24
24
48
24
Trace
Trace
82
d
d
0
Asymmetric oxysulfenylation of unfunctionalized olefins with
external nucleophiles was also investigated with the above cata-
lytic system. However, no reaction was observed when cyclohexene
was treated with acid catalyst 3h, trifluoroethyl benzenesulfenate
(2d), and BnOH. Additional sulfur reagents and Brønsted acids were
thus examined with cyclohexene as substrate. As shown in Table 4,
oxysulfenylation occurred when a stronger acid TsOH was used
(entries 1e3). The enantioselective desymmetrization was also
found to be possible with chiral N-triflyl phosphoramide 3b as
catalyst and sulfenamide 2e5d or 2f as sulfur source (Table 4, entries
5e12). The enantioselectivity varied with nucleophiles and 49% ee
was obtained with PhCOOH at 0 ꢁC (Table 4, entry 11). Additional
symmetric olefins were subsequently examined for the reaction
with N-triflyl phosphoramide 3b, sulfenamide 2e, and PhCOOH
(Table 5, entries 2e7). Up to 50% ee was obtained (Table 5, entry 4).
67
5
Trace
Trace
88
100
68
92
91
85
d
d
55
35
56
46
ꢀ53
61
61
d
9
10
11
12
13
14
88
NRe
a
Reactions were carried out with 1a (0.10 mmol), 2d (0.12 mmol), and
(0.01e0.10 mmol) in CHCl3 (1.0 mL) and toluene (0.5 mL) at ꢀ85 ꢁC.
3
b
Isolated yield.
c
Determined by chiral HPLC (Chiralcel OD-H column).
The stereochemistry indicated is relative stereochemistry.
No reaction.
d
e

2730
H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
Table 4
Table 5
Studies on sulfur reagents, acid catalysts, and nucleophiles
Catalytic asymmetric oxysulfenylation of olefinsa
Entry
1
Substrate 6
Product 9c
Time (h)
30
Yieldd (%)
87
eee (%)
49
Entry
Cat.
2
NuH 7
Time (h)
Yielde,f (%)
eeg (%)
1a
TsOH
TsOH
TsOH
3a4
3b
3b
3b
3b
3b
2d
2e
2f
2e
2e
2e
2e
2e
2e
2f
7a, BnOH
7a, BnOH
7a, BnOH
7a, BnOH
7a, BnOH
24
5
8a, 47
8b, 65
8c, 66
8b, NRh
8b, 79
8d, 51
8e, 91
8f, 95
8g, 94
8h, 89
8g, 87
d
d
d
d
20
20
36
19
42
42
49
2b
3b
19
19
35
48
24
24
24
36
30
4c
5c
6c
7b, PrOH
i
7c
7c, PhOH
7d, HOAc
7e, PhCOOH
7e, PhCOOH
7e, PhCOOH
2
3
20
59
79
73
42
25
8c
9c
10b
11b,d
3b
3b
2e
12c
3b
2e
24
8i, 90
6
4
66
87
77
46
50
25
a
Reactions were carried out with 6a (0.20 mmol), 2d (0.24 mmol), BnOH
(0.40 mmol), and TsOH (0.02 mmol) in CHCl3 (1.0 mL) at 25 ꢁC.
b
With 6a (0.50 mmol), 2e or 2f (0.60 mmol), NuH (1.0 mmol), and TsOH or 3b
(0.05 mmol) in CHCl3 (2.5 mL) at 25 ꢁC.
5b
c
With 6a (0.30 mmol), 2e (0.36 mmol), NuH (0.60 mmol), and 3a4 or 3b
(0.03 mmol) in CHCl3 (1.5 mL) at 25 ꢁC.
d
At 0 ꢁC.
e
The stereochemistry indicated is relative stereochemistry.
Isolated yield.
Determined by chiral HPLC or GC.
No reaction.
f
6
30
36
57
33
g
h
However, no reaction was observed with cis-stilbene under the
reaction conditions (Table 5, entry 7).10 Unsymmetric cis-1-
cyclohexylpropene gave 35% ee (Table 5, entry 8).
7b
NRf
d
The desymmetrization process was also investigated with N-
phenylselenophthalimide (10).21 Compared to sulfenamide 2e, the
Se reagent displayed higher reactivity toward olefins. The reaction
with 10 occurred at room temperature in the absence of N-triflyl
phosphoramide 3b. The background reaction was suppressed when
the reaction temperature was lowered to ꢀ30 ꢁC. As shown in Table
6, the carboxyselenenylation was generally more enantioselective
than the corresponding carboxysulfenylation for cyclic olefins
(Table 5), and up to 84% ee was obtained (Table 6, entry 1). It ap-
pears that the chiral counteranion is a more effective chiral control
element for the nucleophilic opening of seleniranium ion as com-
pared to the corresponding thiiranium ion (Scheme 3).10,22,23 The
oxyselenenylation of cyclohexene (6a) was also investigated with
chiral N-triflyl thiophosphoramide 1220c (Fig. 1), but little reaction
was observed.
8
41
59
35
a
Reactions were carried out with 6 (0.50 mmol), 2e (0.60 mmol), benzoic acid
(1.0 mmol), and 3b (0.05 mmol) in CHCl3 (2.5 mL) at 0 ꢁC.
b
With
6 (0.50 mmol), 2e (0.60 mmol), benzoic acid (1.0 mmol), and 3b
(0.05 mmol) in CHCl3 (2.5 mL) at 25 ꢁC.
c
The stereochemistry indicated is relative stereochemistry.
d
Isolated yield.
Determined by chiral HPLC.
No reaction.
e
f
84% ee, respectively. The carboxyselenenylation has been shown to
be generally more enantioselective than the corresponding car-
boxysulfenylation for the desymmetrization. These results dem-
onstrate that asymmetric oxysulfenylation and oxyselenenylation
of olefins with chiral Brønsted acid are feasible. Further efforts will
be devoted to understanding the mechanism and developing more
effective catalytic systems to improve the enantioselectivity as well
as to expand the substrate scope.
3. Conclusion
In summary, chiral Brønsted acid catalyzed enantioselective
oxysulfenylation and oxyselenenylation of olefins have been ex-
plored. Enantiomerically enriched tetrahydrofurans are formed
with up to 63% ee via sulfetherification of alkenols with dibenzoyl-
D-tartaric acid-based catalyst 3h and trifluoroethyl benzene-
4. Experimental section
sulfenate (2d) as sulfur source. Cyclic olefins can be enantiose-
lectively desymmetrized with N-propylthiosuccinimide (2e) or N-
phenylselenophthalimide (10) and PhCOOH in the presence of
chiral binaphthol derived N-triflyl phosphoramide catalyst 3b,
4.1. General information and materials
All commercially available reagents were used without further
giving chiral
b-carboxyl sulfides and selenides with up to 50% and
purification. All dry solvents were freshly distilled under nitrogen

H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
2731
(0.0872 g, 15% yield). Mp 98e100 ꢁC; [
(film) 1774, 1733, 1245, 1109 cmꢀ1
a
]
20 ꢀ136 (c 0.25, CHCl3); IR
Table 6
D
Catalytic asymmetric oxyselenenylation of olefinsa
;
1H NMR (400 MHz, CDCl3)
d
8.15e8.00 (m, 4H), 7.62e7.50 (m, 2H), 7.49e7.37 (m, 4H), 6.13 (s,
1H), 5.99 (s, 1H), 5.07 (d, J¼8.0 Hz, 1H), 4.18e4.10 (m, 1H),
4.10e3.98 (m, 3H), 3.97e3.85 (m, 2H), 1.46 (s, 3H), 1.40 (s, 3H),
1.06 (s, 3H), 0.87 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 169.7, 165.3,
165.2, 165.1, 133.8, 133.6, 130.3, 130.1, 128.9, 128.6, 128.5, 128.4,
112.5, 109.7, 103.1, 74.5, 73.6, 72.0, 71.5, 71.4, 70.7, 60.2, 27.2, 26.5,
26.0, 25.8; HRMS calcd for C30H31O13 (MꢀHþ): 599.1765; found:
599.1769.
Entry
Substrate 6
Product 11b
Time (h)
Yieldc (%)
eed (%)
1
2
3
4
5
6
6a
6b
6c
6d
6e
6f
11a
11b
11c
11d
11e
11f
46
69
69
69
60
69
71
69
60
72
29
62
84
68
67
71
75
25
4.2.2. Dibenzoyl-
-fructopyranosyl ester (3h). To a stirred solution of 1,2;4,5-di-O-
isopropylidene-
-fructopyranose30 (1.30 g, 5.0 mmol) and
D-tartaric acid mono 1,2;4,5-di-O-isopropylidene-b-
D
b
-
D
D-
(ꢀ)-dibenzoyltartaric anhydride28 (3.40 g, 10.0 mmol) in CHCl3
(50 mL) was added DMAP (0.614 g, 5.0 mmol) at 22 ꢁC. Upon
stirring at 22 ꢁC for 34 h, the reaction mixture was concentrated
and purified by column chromatography (silica gel, eluent: pe-
troleum ether/ethyl acetate/HOAc¼40:10:1 to 20:10:1) to give
a liquid, which was washed with water (50 mLꢃ4) and brine to
remove the acetic acid, dried over Na2SO4, filtered, and concen-
a
Reactions were carried out with 6 (0.50 mmol), 10 (0.60 mmol), benzoic acid
(1.0 mmol), and 3b (0.05 mmol) in CHCl3 (2.5 mL) at ꢀ30 ꢁC.
b
The stereochemistry indicated is relative stereochemistry.
Isolated yield.
Determined by chiral HPLC.
c
d
trated to afford monoester 3h as white foam (0.835 g, 28% yield).
20
Mp 89e92 ꢁC; [
a
;
]
ꢀ70.2 (c 0.44, CHCl3); IR (film) 1773, 1733,
D
1245, 1085 cmꢀ1
1H NMR (400 MHz, CDCl3)
d
8.10 (d, J¼8.0 Hz,
2H), 8.05 (d, J¼7.6 Hz, 2H), 7.61e7.53 (m, 2H), 7.49e7.37 (m, 4H),
6.07 (d, J¼2.8 Hz, 1H), 6.00 (d, J¼2.8 Hz, 1H), 5.16 (d, J¼8.4 Hz, 1H),
4.28e4.20 (m, 1H), 4.16e4.10 (m, 1H), 4.05e3.98 (m, 2H), 3.77 (d,
J¼9.2 Hz, 1H), 3.69 (d, J¼9.2 Hz, 1H), 1.36 (s, 3H), 1.32 (s, 3H), 1.17
Scheme 3.
(s, 3H), 1.14 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 169.9, 166.2,
165.3, 165.2, 133.9, 133.8, 130.4, 129.0, 128.8, 128.7, 128.6, 112.3,
110.0, 103.4, 74.5, 73.9, 72.7, 71.7, 71.5, 71.4, 60.8, 27.7, 26.2, 26.11,
26.06; HRMS calcd for C30H31O13 (MꢀHþ): 599.1765; found:
599.1767.
4.2.3. (Z)-(Dec-4-en-1-yl)benzenesulfenate (5). To a stirred solution
of Et3N (0.223 g, 2.20 mmol) and olefin 1a (0.313 g, 2.00 mmol) in
Et2O (20 mL) was added dropwise benzenesulfenyl chloride
(0.289 g, 2.00 mmol) at room temperature. Upon stirring for
15 min, the reaction mixture was filtered through a plug of Celite
with Et2O as eluent, concentrated, and purified by column chro-
matography (silica gel, eluent: petroleum ether/Et3N¼100:1) to
give compound 5 as colorless oil (0.120 g, 23% yield). IR (film) 1583,
Fig. 1. Chiral Brønsted Acids 3a4 and 12.
from appropriate drying agents. Toluene and Et2O were distilled
from sodium/benzophenone. CHCl3 was distilled from P2O5. Col-
umn chromatography was performed on silica gel (200e300
mesh). 1H NMR spectra were recorded on a 400 MHz NMR spec-
trometer and 13C NMR spectra were recorded on a 100 MHz NMR
spectrometer. IR spectra were recorded on an FT-IR spectrometer.
Melting points were uncorrected. Alkenes 1aec, 6aeg, and chiral
acids 3d, 3e were purchased from commercial suppliers. Alkenes
1deg, 6h, and chiral acids 3a1e4, 3b, 3c, 3feh, and 12 were syn-
thesized according to published procedures (for 1def see: Ref. 24;
for 1g, see: Ref. 25; for 6h, see: Ref. 26; for 3a1e4 see: Ref. 17 and Ref.
27; for 3b see: Ref. 20a; for 3c, see: Ref. 19c; for 3feh, see: Ref. 28;
for 12, see: Ref. 20c). N-Phenylselenophthalimide 10 was synthe-
sized according to Ref. 29.
1477 cmꢀ1
; d 7.44e7.17 (m, 5H),
1H NMR (400 MHz, CDCl3)
5.44e5.29 (m, 2H), 3.84 (t, J¼6.4 Hz, 2H), 2.19e2.09 (m, 2H),
2.09e1.98 (m, 2H), 1.80e1.70 (m, 2H), 1.44e1.23 (m, 6H), 0.92 (t,
J¼6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 141.0,131.3,129.2, 128.5,
126.7, 124.2, 78.3, 31.7, 30.6, 29.6, 27.4, 23.7, 22.8, 14.3; HRMS calcd
for C16H24OS (Mþ): 264.1548; found: 264.1551.
4.3. Representative procedure for chiral acid catalyzed
sulfetherification
4.3.1. 2-[1-(Phenylthio)hexyl]tetrahydrofuran (4a) (Table 3, entry
1). To a stirred solution of chiral acid 3h (0.030 g, 0.050 mmol) and
olefin 1a (0.078 g, 0.50 mmol) in CHCl3/toluene (5.0 mL/2.5 mL)
was added trifluoroethyl benzenesulfenate 2d (0.125 g, 0.60 mmol)
at ꢀ85 ꢁC. Upon stirring at ꢀ85 ꢁC for 48 h, the reaction mixture
was quenched with Et3N (1.0 mL), filtered through a plug of silica
gel with CH2Cl2 (50 mL) as eluent, concentrated, and purified by
column chromatography (silica gel, eluent: petroleum ether/ethyl
acetate¼50:1) to give compound 4a as colorless oil (0.117 g, 89%
yield). The sample was subjected to chiral HPLC (Chiralcel OD-H
column) to determine the ee.
4.2. Preparation of acid 3g, 3h, and compound 5
4.2.1. Dibenzoyl-
L
-tartaric acid mono 1,2;4,5-di-O-isopropylidene-
b
-
D
-fructopyranosyl ester (3g). To a stirred solution of 1,2;4,5-di-O-
isopropylidene-
b
-
D
-fructopyranose30 (0.651 g, 2.50 mmol) and
L
-
(þ)-dibenzoyltartaric anhydride28 (0.340 g, 1.00 mmol) in CHCl3
(10 mL) was added DMAP (0.0613 g, 0.50 mmol) at 20 ꢁC. Upon
stirring at 20 ꢁC for 12 h and at 50 ꢁC for 10 h, the reaction mix-
ture was concentrated and purified by column chromatography
(silica gel, eluent: petroleum ether/ethyl acetate/HOAc¼40:10:1
to 20:10:1) to give a liquid, which was washed with water
(50 mLꢃ3) and brine to remove acetic acid, dried over Na2SO4,
filtered, and concentrated to give monoester 3g as white foam
4.3.2. 2-[2,2-Dimethyl-1-(phenylthio)propyl]tetrahydrofuran
(4d)
(Table 3, entry 4). To a stirred solution of chiral acid 3h (0.060 g,

2732
H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
0.10 mmol) and olefin 1d (0.071 g, 0.50 mmol) in CHCl3 (5.0 mL)
was added trifluoroethyl benzenesulfenate 2d (0.125 g, 0.60 mmol)
at ꢀ60 ꢁC. Upon stirring at ꢀ60 ꢁC for 48 h, the reaction mixture
was quenched with Et3N (1.0 mL), filtered through a plug of silica
gel with CH2Cl2 (50 mL) as eluent, concentrated, and purified by
column chromatography (silica gel, eluent: petroleum ether/ethyl
acetate¼50:1) to give compound 4d as colorless oil (0.093 g, 74%
yield). The sample was subjected to chiral HPLC (Chiralcel OD-H
column) to determine the ee.
32.1, 31.4, 29.75, 29.71, 29.5, 28.6, 27.5, 26.4, 22.9, 14.3; HRMS calcd
for C20H32OS (Mþ): 320.2174; found:320.2177.
4.3.9. 2,2-Dimethyl-5-[1-(phenylthio)hexyl]tetrahydrofuran
(4g)
(Table 3, entry 7). Colorless oil; [
a
]
D
20 þ16.1 (c 1.12, CHCl3) (44% ee);
IR (film) 1458, 1026 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
7.41 (d,
J¼7.6 Hz, 2H), 7.25 (t, J¼7.6 Hz, 2H), 7.17 (t, J¼7.6 Hz, 1H), 4.22e4.10
(m, 1H), 3.23e3.10 (m, 1H), 2.09e1.97 (m, 1H), 1.96e1.85 (m, 1H),
1.84e1.76 (m, 1H), 1.76e1.52 (m, 3H), 1.51e1.38 (m, 2H), 1.31e1.22
(m, 7H), 1.20 (s, 3H), 0.87 (t, J¼6.8 Hz, 3H); 13C NMR (100 MHz,
4.3.3. 2-[1-(Phenylthio)hexyl]tetrahydrofuran (4a) (Table 3, entry
CDCl3) d 136.8, 131.2, 128.9, 126.4, 81.5, 80.3, 53.2, 38.8, 32.0, 30.5,
1). Colorless oil; [
a
]
20 þ16.1 (c 0.93, CHCl3) (61% ee); IR (film) 1479,
28.7, 28.5, 28.0, 27.4, 22.7, 14.2; HRMS calcd for C18H28OS (Mþ):
292.1861; found: 292.1864.
D
1057 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.42 (d, J¼7.6 Hz, 2H), 7.26
(t, J¼7.6 Hz, 2H), 7.18 (t, J¼7.6 Hz, 1H), 4.07e3.98 (m, 1H), 3.96e3.86
(m, 1H), 3.80e3.70 (m, 1H), 3.22e3.13 (m, 1H), 2.03e1.68 (m, 5H),
1.67e1.40 (m, 3H), 1.35e1.19 (m, 4H), 0.87 (t, J¼6.8 Hz, 3H); 13C
4.4. Representative oxysulfenylation procedure for Table 4
(entry 5)
NMR (100 MHz, CDCl3)
d 136.5, 131.5, 129.0, 126.6, 81.1, 68.9, 53.5,
32.0, 31.4, 28.6, 27.2, 26.4, 22.7, 14.2; HRMS calcd for C16H24OS
To a stirred solution of cyclohexene (0.0246 g, 0.30 mmol), N-
propylthiosuccinimide 2e (0.0624 g, 0.36 mmol), and BnOH
(0.0649 g, 0.60 mmol) in CHCl3 (1.5 mL) was added (S)-N-triflyl
phosphoramide 3b (0.0265 g, 0.030 mmol) at 25 ꢁC. Upon stirring at
25 ꢁC for 35 h, the reaction mixture was filtered through a plug of
silica gel with CH2Cl2 (50 mL) as eluent, concentrated, and purified
by flash chromatography (silica gel, eluent: petroleum ether/ethyl
acetate¼70:1) to give compound 8b as pale yellowoil (0.063 g, 79%).
(Mþ): 264.1548; found: 264.1551.
4.3.4. 2-[1-(Phenylthio)ethyl]tetrahydrofuran (4b) (Table 3, entry
2). Colorless oil; [
a
]
20 þ2.8 (c 1.06, CHCl3) (51% ee); IR (film) 1583,
D
1479, 1061 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.43 (d, J¼7.2 Hz, 2H),
7.28 (t, J¼7.2 Hz, 2H), 7.21 (t, J¼7.2 Hz, 1H), 3.99e3.87 (m, 2H),
3.82e3.73 (m, 1H), 3.42e3.31 (m, 1H), 2.04e1.71 (m, 4H), 1.28 (d,
J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 135.3, 132.0, 129.0,
126.9, 81.7, 68.9, 47.3, 28.5, 26.4, 17.3; HRMS calcd for C12H16OS
4.4.1. trans-1-Benzyloxy-2-phenylthiocyclohexane (8a) (Table 4, en-
try 1). Colorless oil; IR (film) 1453, 1092; 1H NMR (400 MHz, CDCl3)
(Mþ): 208.0922; found: 208.0924.
d
7.46e7.15 (m, 10H), 4.63 (d, J¼11.6 Hz, 1H), 4.57 (d, J¼11.6 Hz, 1H),
4.3.5. 2-[1-(Phenylthio)propyl]tetrahydrofuran (4c) (Table 3, entry
3.39 (td, J¼8.4, 4.0 Hz, 1H), 3.27 (td, J¼9.2, 4.0 Hz, 1H), 2.20e1.98
(m, 2H), 1.82e1.58 (m, 2H), 1.53e1.38 (m, 2H), 1.37e1.20 (m, 2H);
3). Colorless oil; [
a
]
20 þ26.8 (c 1.36, CHCl3) (53% ee); IR (film) 1583,
D
1479, 1062 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.42 (d, J¼7.2 Hz, 2H),
13C NMR (100 MHz, CDCl3)
d 139.0, 135.7, 132.0, 128.9, 128.5, 127.9,
7.26 (t, J¼7.2 Hz, 2H), 7.18 (t, J¼7.2 Hz, 1H), 4.09e3.99 (m, 1H),
3.96e3.86 (m, 1H), 3.81e3.70 (m, 1H), 3.11 (dt, J¼8.4, 4.8 Hz, 1H),
2.04e1.75 (m, 5H),1.61e1.48 (m,1H),1.09 (t, J¼7.2 Hz, 3H); 13C NMR
127.6, 126.7, 80.0, 71.4, 51.3, 31.4, 30.5, 24.7, 23.4; HRMS calcd for
C19H22OS (Mþ): 298.1391; found: 298.1396.
(100 MHz, CDCl3)
d
136.5, 131.5, 129.0, 126.6, 80.9, 68.9, 55.4, 28.8,
4.4.2. trans-1-Benzyloxy-2-propylthiocyclohexane (8b) (Table 4, en-
26.4, 24.6, 12.2; HRMS calcd for C13H18OS (Mþ): 222.1078; found:
222.1081.
try 5). Pale yellow oil; [
a]
20 ꢀ4.8 (c 0.60, CHCl3 ) (20% ee); IR (film)
D
1453, 1095 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
7.42e7.24 (m, 5H),
4.65 (d, J¼11.6 Hz, 1H), 4.59 (d, J¼11.6 Hz, 1H), 3.32 (td, J¼8.4,
3.6 Hz, 1H), 2.72 (td, J¼8.8, 3.6 Hz, 1H), 2.59 (t, J¼7.6 Hz, 2H),
2.15e2.00 (m, 2H), 1.79e1.50 (m, 4H), 1.48e1.19 (m, 4H), 0.95 (t,
4.3.6. 2-[2,2-Dimethyl-1-(phenylthio)propyl]tetrahydrofuran
(4d)
(Table 3, entry 4). Colorless oil; [
a]
20 þ21.7 (c 1.01, CHCl3) (31% ee);
D
IR (film) 1583,1479,1084 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.39 (d,
J¼7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 139.2, 128.5, 128.0,
J¼7.2 Hz, 2H), 7.23 (t, J¼7.2 Hz, 2H), 7.12 (t, J¼7.2 Hz, 1H), 4.40 (t,
J¼7.2 Hz, 1H), 4.00e3.85 (m, 1H), 3.83e3.74 (m, 1H), 3.01 (s, 1H),
2.10e1.90 (m, 3H), 1.90e1.73 (m, 1H), 1.09 (s, 9H); 13C NMR (100
127.6, 81.8, 71.5, 48.6, 34.3, 31.7, 30.7, 25.0, 23.6, 13.8; HRMS calcd
for C16H24NaOS (MþNaþ): 287.1440; found: 287.1436.
MHz, CDCl3)
d
140.4, 129.6, 129.0, 125.6, 78.4, 69.6, 66.7, 37.4, 31.9,
4.4.3. trans-1-Benzyloxy-2-benzylthiocyclohexane (8c) (Table 4, en-
try 3). Colorless oil; IR (film) 1453, 1093 cmꢀ1; 1H NMR (400 MHz,
28.9, 26.2; HRMS calcd for C15H22OS (Mþ): 250.1391; found:
250.1394.
CDCl3)
d
7.42e7.18 (m, 10H), 4.61 (d, J¼11.6 Hz, 1H), 4.56 (d,
J¼11.6 Hz, 1H), 3.88 (d, J¼13.2 Hz, 1H), 3.82 (d, J¼13.2 Hz, 1H), 3.35
(td, J¼8.4, 3.6 Hz,1H), 2.70 (td, J¼9.2, 4.0 Hz,1H), 2.14e1.98 (m, 2H),
1.78e1.58 (m, 2H), 1.45e1.19 (m, 4H); 13C NMR (100 MHz, CDCl3)
4.3.7. 2-[3-Phenyl-1-(phenylthio)propyl]tetrahydrofuran (4e) (Table
20
3, entry 5). Colorless oil; [
a
]
;
þ6.1 (c 0.99, CHCl3) (50% ee); IR
D
(film) 1583, 1480, 1057 cmꢀ1
1H NMR (400 MHz, CDCl3)
d
7.39 (d,
d 139.15,139.11,129.2, 128.6,128.5,127.9,127.7,127.0, 82.1, 71.4, 47.9,
J¼7.2 Hz, 2H), 7.30e7.10 (m, 8H), 4.09e4.00 (m, 1H), 3.94e3.86 (m,
1H), 3.80e3.70 (m, 1H), 3.20 (dt, J¼9.2, 4.4 Hz, 1H), 3.03e2.90 (m,
1H), 2.85e2.71 (m, 1H), 2.16e1.73 (m, 6H); 13C NMR (100 MHz,
36.8, 31.3, 30.7, 25.0, 23.5; HRMS calcd for C20H25OS (MþHþ):
313.1621; found: 313.1620.
CDCl3)
d
142.0, 136.1, 131.5, 129.0, 128.7, 128.5, 126.7, 126.1, 81.0,
4.4.4. trans-1-Isopropoxy-2-propylthiocyclohexane (8d) (Table 4,
69.0, 52.7, 33.6, 33.1, 28.6, 26.4; HRMS calcd for C19H22OS (Mþ):
298.1391; found: 298.1395.
entry 6). Pale yellow oil; [
a
]
D
20 ꢀ5.8 (c 1.10, CHCl3) (20% ee); IR (film)
1448, 1084 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
3.75 (septet,
J¼6.4 Hz, 1H), 3.23e3.14 (m, 1H), 2.68e2.51 (m, 3H), 2.14e1.91 (m,
2H), 1.76e1.52 (m, 4H), 1.42e1.20 (m, 4H), 1.18 (d, J¼6.4 Hz, 3H), 1.14
(d, J¼6.4 Hz, 3H), 0.97 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
4.3.8. 2-[1-(Phenylthio)decyl]tetrahydrofuran (4f) (Table 3, entry
6). Colorless oil; [
a
]
20 þ10.1 (c 0.94, CHCl3) (63% ee); IR (film) 1479,
D
1059 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.41 (d, J¼7.6 Hz, 2H), 7.26
d 80.0, 70.6, 49.2, 34.2, 32.5, 32.2, 25.3, 24.0, 23.6, 23.4, 22.7, 13.8;
(t, J¼7.6 Hz, 2H), 7.18 (t, J¼7.6 Hz, 1H), 4.08e3.97 (m, 1H), 3.97e3.85
(m, 1H), 3.75 (q, J¼6.8 Hz, 1H), 3.25e3.13 (m, 1H), 2.03e1.67 (m,
5H),1.66e1.37 (m, 3H),1.37e1.11 (m,12H), 0.88 (t, J¼7.2 Hz, 3H); 13C
HRMS calcd for C12H24OS (Mþ): 216.1548; found: 216.1551.
4.4.5. trans-1-Phenoxy-2-propylthiocyclohexane (8e) (Table 4, entry
NMR (100 MHz, CDCl3)
d
136.5, 131.4, 129.0, 126.6, 81.0, 68.9, 53.5,
7). Colorless oil; [
a]
20 ꢀ5.6 (c 0.98, CHCl3) (36% ee); IR (film) 1599,
D

H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
2733
1493, 1239 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
7.31e7.22 (m, 2H),
23.1, 13.7; HRMS calcd for C15H21O2S (MþHþ): 265.1257; found:
7.00e6.89 (m, 3H), 4.19 (td, J¼8.0, 3.6 Hz, 1H), 2.90 (td, J¼8.4,
265.1256.
4.0 Hz, 1H), 2.71e2.57 (m, 2H), 2.20e2.07 (m, 2H), 1.82e1.30 (m,
8H), 0.96 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d
158.0, 129.7,
4.5.3. trans-2-(Propylthio)cycloheptyl benzoate (9c) (Table 5, entry
121.1, 116.5, 80.6, 47.5, 34.6, 31.1, 30.2, 24.6, 23.6, 23.2, 13.8; HRMS
3). Colorless oil; [
a
]
20 ꢀ15.3 (c 1.66, CHCl3) (25% ee); IR (film) 1716,
D
calcd for C15H23OS (MþHþ): 251.1464; found: 251.1466.
1271 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.06 (d, J¼7.2 Hz, 2H), 7.56
(t, J¼7.6 Hz, 1H), 7.45 (t, J¼7.6 Hz, 2H), 5.35e5.24 (m, 1H), 3.14e3.05
(m, 1H), 2.65e2.53 (m, 2H), 2.18e2.08 (m, 1H), 2.04e1.93 (m, 2H),
1.89e1.48 (m, 9H), 0.95 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
4.4.6. trans-2-(Propylthio)cyclohexyl acetate (8f) (Table 4, entry
20
8). Colorless oil; [
a
]
D
ꢀ0.1 (c 0.87, CHCl3) (19% ee); IR (film) 1740,
1237, 1036 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
4.80e4.67 (m, 1H),
d 165.9, 133.1, 131.0, 129.8, 128.6, 78.2, 49.5, 33.8, 31.4, 30.8, 28.8,
2.70e2.60 (m, 1H), 2.60e2.48 (m, 2H), 2.12e1.97 (m, 2H), 2.07 (s,
25.4, 23.3, 22.3, 13.7; HRMS calcd for C17H25O2S (MþHþ): 293.1570;
3H), 1.78e1.19 (m, 8H), 0.97 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz,
found: 293.1572.
CDCl3) d 170.5, 75.4, 47.4, 33.4, 31.9, 31.0, 25.0, 23.6, 23.5, 21.5, 13.7;
HRMS calcd for C11H20NaO2S (MþNaþ): 239.1076; found: 239.1072.
4.5.4. trans-2-(Propylthio)cyclooctyl benzoate (9d) (Table 5, entry
4). Colorless oil; [
a
]
20 ꢀ32.9 (c 0.94, CHCl3) (50% ee); IR (film) 1716,
D
4.4.7. trans-2-(Benzylthio)cyclohexyl benzoate (8h) (Table 4, entry
1275 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.06 (d, J¼6.8 Hz, 2H), 7.55
10). Pale yellow oil; [
a
]
D
20 ꢀ1.7 (c 3.1, CHCl3) (42% ee); IR (film) 1716,
(t, J¼7.2 Hz, 1H), 7.44 (t, J¼7.6 Hz, 2H), 5.28e5.18 (m, 1H), 3.18e3.08
(m, 1H), 2.60e2.48 (m, 2H), 2.20e2.08 (m, 1H), 2.05e1.42 (m, 13H),
1275 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.97 (d, J¼7.2 Hz, 2H), 7.46
(t, J¼7.2 Hz, 1H), 7.35 (t, J¼7.6 Hz, 2H), 7.29e7.07 (m, 5H), 5.06e4.94
(m, 1H), 3.74 (d, J¼13.2 Hz, 1H), 3.69 (d, J¼13.2 Hz, 1H), 2.80e2.67
(m, 1H), 2.17e1.93 (m, 2H), 1.62e1.10 (m, 6H); 13C NMR (100 MHz,
0.91 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 166.0, 132.9,
131.0, 129.8, 128.5, 78.9, 48.8, 34.0, 31.2, 29.5, 26.2, 25.8, 25.7, 25.0,
23.3, 13.7; HRMS calcd for C18H27O2S (MþHþ): 307.1726; found:
307.1725.
CDCl3)
d 165.9, 138.6, 133.0, 130.8, 129.8, 129.1, 128.6, 128.5, 127.1,
75.5, 46.8, 35.9, 31.4, 30.6, 24.7, 23.4; HRMS calcd for C20H23O2S
(MþHþ): 327.1413; found: 327.1415.
4.5.5. trans-3-(Propylthio)-1,2,3,4-tetrahydronaphthalen-2-yl ben-
zoate (9e) (Table 5, entry 5). Colorless oil; [
a
]
D
20 ꢀ15.1 (c 1.48, CHCl3)
4.4.8. trans-2-(Propylthio)cyclohexyl 2,6-dimethyl benzoate (8i)
(25% ee); IR (film) 1717, 1262 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
(Table 4, entry 12). Colorless oil; [
a
]
D
20 ꢀ1.5 (c 1.16, CHCl3 ) (6% ee);
d
8.02 (d, J¼7.2 Hz, 2H), 7.56 (t, J¼7.6 Hz, 1H), 7.43 (t, J¼7.6 Hz, 2H),
IR (film) 1725, 1265, 1072 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
7.17 (t,
7.22e7.05 (m, 4H), 5.58e5.49 (m, 1H), 3.58e3.36 (m, 3H),
3.08e2.91 (m, 2H), 2.77e2.61 (m, 2H), 1.75e1.57 (m, 2H), 1.00 (t,
J¼7.6 Hz, 1H), 7.02 (d, J¼7.6 Hz, 2H), 5.04 (td, J¼9.2, 4.0 Hz, 1H), 2.74
(td, J¼9.6, 4.0 Hz, 1H), 2.62e2.48 (m, 2H), 2.37 (s, 6H), 2.32e2.22
(m, 1H), 2.19e2.10 (m, 1H), 1.81e1.68 (m, 2H), 1.62e1.25 (m, 6H),
J¼7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 166.1, 133.8,133.2,133.0,
130.5, 129.8, 129.2, 128.9, 128.6, 126.6, 126.4, 72.7, 42.9, 33.8, 33.4,
32.6, 23.4, 13.7; HRMS calcd for C20H23O2S (MþHþ): 327.1413;
found: 327.1417.
0.95 (t, J¼7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d 169.7, 134.8,
134.6, 129.3, 127.7, 75.9, 47.3, 33.2, 32.3, 31.2, 25.0, 23.7, 23.4, 19.9,
13.8; HRMS calcd for C18H26NaO2S (MþNaþ): 329.1546; found:
329.1550.
4.5.6. threo-5-(Propylthio)octan-4-yl benzoate (9f) (Table 5, entry
6). Pale yellow oil; [
a
]
20 þ4.8 (c 1.45, CHCl3) (33% ee); IR (film) 1717,
D
4.5. Representative procedure for desymmetrization of olefin
with N-propylthiosuccinimide (Table 5, entry 4)
1268 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.05 (d, J¼7.6 Hz, 2H), 7.57
(t, J¼7.2 Hz,1H), 7.45 (t, J¼7.6 Hz, 2H), 5.30e5.22 (m,1H), 2.86e2.78
(m, 1H), 2.70e2.52 (m, 2H), 1.92e1.55 (m, 6H), 1.50e1.29 (m, 4H),
1.01 (t, J¼7.6 Hz, 3H), 0.95 (t, J¼7.6 Hz, 3H), 0.89 (t, J¼7.2 Hz, 3H);
To a stirred solution of cyclooctene (0.0551 g, 0.50 mmol), N-
propylthiosuccinimide 2e (0.1040 g, 0.60 mmol), and PhCO2H
(0.1221 g, 1.0 mmol) in CHCl3 (2.5 mL) was added (S)-N-triflyl
phosphoramide 3b (0.0442 g, 0.050 mmol) at 0 ꢁC. Upon stirring
at 0 ꢁC for 66 h, the reaction mixture was filtered through a plug
of silica gel with CH2Cl2 (50 mL) as eluent, concentrated, and
purified by flash chromatography (silica gel, eluent: petroleum
ether/ethyl acetate¼70:1) to give compound 9d as colorless oil
(0.1173 g, 77%).
13C NMR (100 MHz, CDCl3)
d 166.5, 133.1, 130.7, 129.8, 128.6, 77.1,
49.0, 34.5, 33.2, 32.0, 23.6, 21.0, 19.7, 14.2, 14.1, 13.7; HRMS calcd for
C18H29O2S (MþHþ): 309.1883; found: 309.1881.
4.5.7. threo-1-Cyclohexyl-1-(propylthio)propan-2-yl benzoate (9h)
(Table 5, entry 8). Colorless oil; [
a
]
20 ꢀ1.0 (c 0.99, CHCl3) (35% ee); IR
D
(film) 1717,1273 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.04 (d, J¼7.2 Hz,
2H), 7.55 (t, J¼7.6 Hz, 1H), 7.44 (t, J¼7.6 Hz, 2H), 5.50e5.41 (m, 1H),
2.68e2.52 (m, 2H), 2.51e2.45 (m, 1H), 2.02e1.94 (m, 1H), 1.86e1.56
(m, 7H), 1.48 (d, J¼6.0 Hz, 3H), 1.33e1.09 (m, 5H), 0.98 (t, J¼7.2 Hz,
4.5.1. trans-2-(Propylthio)cyclohexyl benzoate (9a/8g) (Table 5, entry
20
1). Pale yellow oil; [
a
]
D
ꢀ44.3 (c 1.16, CHCl3 ) (49% ee); IR (film)
3H); 13C NMR (100 MHz, CDCl3)
d 166.1, 133.0, 130.9, 129.9, 128.6,
1717, 1274 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.06 (d, J¼7.6 Hz, 2H),
72.9, 58.1, 40.8, 36.3, 31.7, 30.8, 26.7, 26.6, 26.5, 23.6,18.5,13.7; HRMS
7.56 (t, J¼7.6 Hz, 1H), 7.44 (t, J¼7.6 Hz, 2H), 5.04 (td, J¼8.0, 4.0 Hz,
1H), 2.86 (td, J¼8.4, 4.0 Hz, 1H), 2.68e2.50 (m, 2H), 2.22e2.10 (m,
2H), 1.82e1.68 (m, 2H), 1.68e1.32 (m, 6H), 0.93 (t, J¼7.2 Hz, 3H); 13C
calcd for C19H28NaO2S (MþNaþ): 343.1702; found: 343.1706.
4.6. Representative procedure for desymmetrization of olefin
with N-phenylselenophthalimide (Table 6, entry 1)
NMR (100 MHz, CDCl3) d 166.0, 133.0, 130.9, 129.8, 128.5, 75.8, 47.1,
33.7, 31.5, 30.4, 24.6, 23.5, 23.3, 13.7; HRMS calcd for C16H23O2S
(MþHþ): 279.1413; found: 279.1410.
To a stirred solution of (S)-N-triflyl phosphoramide 3b (0.0442 g,
0.050 mmol),
N-phenylselenophthalimide
(10)
(0.1813 g,
4.5.2. trans-2-(Propylthio)cyclopentyl benzoate (9b) (Table 5, entry
0.60 mmol), and PhCO2H (0.1221 g, 1.0 mmol) in CHCl3 (2.5 mL) at
ꢀ30 ꢁC was added cyclohexene (0.0411 g, 0.50 mmol). Upon stir-
ring at ꢀ30 ꢁC for 46 h, the reaction mixture was quenched with
Et3N (2.0 mL), filtered through a plug of silica gel with CH2Cl2
(50 mL) as eluent, concentrated, and purified by flash chromatog-
raphy (silica gel, eluent: petroleum ether/ethyl acetate¼70:1 to
40:1) to give compound 11a as pale yellow oil (0.1273 g, 71%) (N-
20
2). Brown oil; [
a
]
ꢀ20.8 (c 0.96, CHCl3 ) (42% ee); IR (film) 1719,
D
1262 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
8.01 (d, J¼7.6 Hz, 2H), 7.56
(t, J¼7.6 Hz,1H), 7.44 (t, J¼7.6 Hz, 2H), 5.38e5.30 (m,1H), 3.34e3.25
(m, 1H), 2.78e2.50 (m, 2H), 2.35e2.17 (m, 2H), 1.92e1.78 (m, 3H),
1.77e1.52 (m, 3H), 0.99 (t, J¼7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3)
d
166.2, 133.1, 130.7, 129.7, 128.5, 82.4, 49.2, 34.2, 31.5, 31.1, 23.2,

2734
H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
Phenylselenophthalimide was synthesized according to the pro-
cedure reported in Ref. 29. Its purity is crucial to the enantiose-
lectivity of the reaction.).
Science Foundation of China (21172221), and the Chinese Academy
of Sciences for the financial support.
Supplementary data
4.6.1. trans-2-(Phenylseleno)cyclohexyl benzoate (11a) (Table 6, en-
try 1). Pale yellow oil; [
a
]
D
20 ꢀ81.4 (c 1.07, CHCl3) (84% ee); IR (film)
Supplementary data related to this article can be found online at
doi:10.1016/j.tet.2012.01.006.
1716, 1267 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
7.98e7.93 (m, 2H),
7.58e7.49 (m, 3H), 7.39 (t, J¼8.0 Hz, 2H), 7.26e7.18 (m, 3H), 5.08 (td,
J¼8.8, 4.0 Hz, 1H), 3.44e3.35 (m, 1H), 2.28e2.16 (m, 2H), 1.82e1.31
References and notes
(m, 6H); 13C NMR (100 MHz, CDCl3)
d 165.9, 135.4, 132.9, 130.7,
129.9, 129.1, 128.7, 128.4, 127.8, 76.0, 46.3, 32.4, 31.6, 25.8, 23.7;
1. For leading reviews on electrophilic sulfur and selenium additions to olefins,
see: (a) Rayner, C. M. In Organosulfur Chemistry: Synthetic Aspects; Page, P., Ed.;
Academic: London, 1995; p 89; (b) Petragnani, N.; Stefani, H. A.; Valduga, C. J.
Tetrahedron 2001, 57, 1411; (c) Freudendahl, D. M.; Shahzad, S. A.; Wirth, T. Eur. J.
Org. Chem. 2009, 11, 1649; (d) Mukherjee, A. J.; Zade, S. S.; Singh, H. B.; Sunoj, R.
B. Chem. Rev. 2010, 110, 4357.
HRMS calcd for C19H20O2Se (Mþ): 360.0629; found: 360.0632.
4.6.2. trans-2-(Phenylseleno)cyclopentyl benzoate (11b) (Table 6,
20
entry 2). Brown oil; [
a]
ꢀ53.7 (c 1.11, CHCl3) (68% ee); IR (film)
D
1717, 1270 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d 7.96e7.91 (m, 2H),
2. For a leading reference on chiral sulfur and selenium reagent-mediated re-
€
actions, see: Burgler, F. W.; Fragale, G.; Wirth, T. ARKIVOC 2007, 21.
7.63e7.57 (m, 2H), 7.56e7.48 (m,1H), 7.39 (t, J¼7.6 Hz, 2H), 7.27e7.19
3. For a leading review on chiral selenium reagent-mediated reactions, see: Wirth,
T. Angew. Chem., Int. Ed. 2000, 39, 3740.
4. For leading references on chiral Lewis base-catalyzed selenoetherification and
thiofunctionalization of alkenes, see: (a) Denmark, S. E.; Kalyani, D.; Collins, W.
R. J. Am. Chem. Soc. 2010, 132, 15752; (b) Denmark, S. E.; Kornfilt, D. J. P.; Vogler,
T. J. Am. Chem. Soc. 2011, 133, 15308.
(m, 3H), 5.42e5.34 (m, 1H), 3.83e3.72 (m, 1H), 2.37e2.24 (m, 2H),
1.90e1.73 (m, 4H); 13C NMR (100 MHz, CDCl3)
d 166.0, 134.4, 133.0,
130.6, 129.7, 129.4, 129.2, 128.4, 127.7, 82.3, 46.2, 31.4, 31.2, 22.8;
HRMS calcd for C18H18O2Se (Mþ): 346.0472; found: 346.0475.
5. (a) Shi, Y. Acc. Chem. Res. 2004, 37, 488; (b) Du, H.; Zhao, B.; Shi, Y. J. Am. Chem.
Soc. 2007, 129, 762; (c) Wang, H.; Huang, D.; Cheng, D.; Li, L.; Shi, Y. Org. Lett.
2011, 13, 1650; (d) Huang, D.; Wang, H.; Guan, H.; Huang, H.; Shi, Y. Org. Lett.
2011, 13, 1548; (e) Huang, D.; Wang, H.; Xue, F.; Guan, H.; Li, L.; Peng, X.; Shi, Y.
Org. Lett. 2011, 13, 6350.
6. For leading references on acid-promoted addition of RS to olefins with RSSR or
RSOR reagents, see: (a) Trost, B. M.; Ochiai, M.; McDougal, P. G. J. Am. Chem. Soc.
1978, 100, 7103; (b) Edstrom, E. D.; Livinghouse, T. J. Am. Chem. Soc. 1986, 108,
1334; (c) Ito, Y.; Ogawa, T. Tetrahedron Lett. 1987, 28, 2723; (d) Taniguchi, N. J.
Org. Chem. 2006, 71, 7874; (e) Yamagiwa, N.; Suto, Y.; Torisawa, Y. Bioorg. Med.
Chem. Lett. 2007, 17, 6197.
7. For leading references on acid-promoted addition of RS or RSe to olefins with
RSeN or RSeeN reagents, see: (a) Nicolaou, K. C.; Claremon, D. A.; Barnette, W.
E.; Seitz, S. P. J. Am. Chem. Soc. 1979, 101, 3704; (b) Caserio, M. C.; Kim, J. K. J. Am.
Chem. Soc. 1982, 104, 3231; (c) Brownbridge, P. Tetrahedron Lett. 1984, 25, 3759;
(d) Benati, L.; Montevecchi, P. C.; Spagnolo, P. Tetrahedron 1986, 42, 1145; (e)
Brownbridge, P. J. Chem. Soc., Chem. Commun. 1987, 1280.
8. For leading references on enantiomerically enriched thiiranium ions, see: (a)
Branchaud, B. P.; Blanchette, H. S. Tetrahedron Lett. 2002, 43, 351; (b) Denmark,
S. E.; Vogler, T. Chem.dEur. J. 2009, 15, 11737.
4.6.3. trans-2-(Phenylseleno)cycloheptyl benzoate (11c) (Table 6,
entry 3). Colorless oil; [
a]
20 ꢀ46.7 (c 1.13, CHCl3) (67% ee); IR (film)
D
1717, 1110 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d
8.02e7.94 (m, 2H),
7.60e7.48 (m, 3H), 7.39 (t, J¼7.6 Hz, 2H), 7.24e7.17 (m, 3H), 5.36 (td,
J¼7.2, 3.6 Hz, 1H), 3.66e3.59 (m, 1H), 2.28e2.16 (m, 1H), 2.07e1.89
(m, 2H), 1.88e1.45 (m, 7H); 13C NMR (100 MHz, CDCl3)
d 165.7,
135.0, 132.9, 130.8, 129.8, 129.4, 129.1, 128.4, 127.7, 78.7, 48.9, 32.0,
31.8, 28.4, 26.6, 22.3; HRMS calcd for C20H22O2Se (Mþ): 374.0785;
found: 374.0789.
4.6.4. trans-2-(Phenylseleno)cyclooctyl benzoate (11d) (Table 6, en-
20
try 4). Colorless oil; [
a
]
D
ꢀ37.5 (c 1.06, CHCl3) (71% ee); IR (film)
1713, 1110 cmꢀ1
;
1H NMR (400 MHz, CDCl3)
d 7.94e7.88 (m, 2H),
7.60e7.48 (m, 3H), 7.38 (t, J¼8.0 Hz, 2H), 7.23e7.15 (m, 3H),
5.45e5.36 (m,1H), 3.77e3.70 (m, 1H), 2.35e2.20 (m,1H), 2.05e1.44
9. For a leading reference on studies of stability of thiiranium ions, see: Denmark,
S. E.; Collins, W. R.; Cullen, M. D. J. Am. Chem. Soc. 2009, 131, 3490.
10. For a leading reference on chiral anion-mediated asymmetric ring opening of
(m, 11H); 13C NMR (100 MHz, CDCl3)
d 165.9, 135.1, 132.8, 130.7,
129.8, 129.0, 128.3, 127.5, 79.1, 48.8, 32.0, 29.9, 26.5, 26.2, 25.7, 25.0;
meso-episulfonium ions generated from b-alkylthio trichloroacetimidate, see:
HRMS calcd for C21H24O2Se (Mþ): 388.0942; found: 388.0946.
Hamilton, G. L.; Kanai, T.; Toste, F. D. J. Am. Chem. Soc. 2008, 130, 14984.
11. For leading references on theoretical studies on selenenylation with chiral se-
lenium reagents, see: (a) Wang, X.; Houk, K. N.; Spichty, M.; Wirth, T. J. Am.
Chem. Soc. 1999, 121, 8567; (b) Spichty, M.; Fragale, G.; Wirth, T. J. Am. Chem. Soc.
2000, 122, 10914.
12. For a leading reference on mechanistic study of selenolactonization, see:
Denmark, S. E.; Edwards, M. G. J. Org. Chem. 2006, 71, 7293.
13. Shimada, H.; Kikuchi, S.; Okuda, S.; Haraguchi, K.; Tanaka, H. Tetrahedron 2009,
65, 6008.
14. Dubey, R.; Polaske, N. W.; Nichol, G. S.; Olenyuk, B. Tetrahedron Lett. 2009, 50,
4310.
15. Chang, L. L.; Denney, D. B.; Denney, D. Z.; Kazior, R. J. J. Am. Chem. Soc. 1977, 99,
2293.
4.6.5. trans-3-(Phenylseleno)-1,2,3,4-tetrahydronaphthalen-2-yl
benzoate (11e) (Table 6, entry 5). White solid; mp 90 ꢁC; [
a
]
20 ꢀ65.0
D
(c 1.02, CHCl3 ) (75% ee); IR (film) 1716, 1267 cmꢀ1
(400 MHz, CDCl3)
;
1H NMR
d
7.97e7.91 (m, 2H), 7.64e7.49 (m, 3H), 7.43e7.35
(m, 2H), 7.30e7.23 (m, 3H), 7.19e7.05 (m, 4H), 5.54e5.47 (m, 1H),
3.96e3.87 (m, 1H), 3.62e3.45 (m, 2H), 3.12e2.90 (m, 2H); 13C NMR
(100 MHz, CDCl3)
d 166.0, 134.8, 134.0, 133.2, 132.9, 130.4, 129.9,
129.4, 129.3, 128.8, 128.5, 128.4, 128.0, 126.7, 126.5, 72.7, 41.3, 33.9,
33.5; HRMS calcd for C23H20O2Se (Mþ): 408.0629; found: 408.0633.
16. Denney, D. B.; Denney, D. Z.; Hammond, P. J.; Wang, Y. J. Am. Chem. Soc. 1981,
103, 1785.
17. Storer, R. I.; Carrera, D. E.; Ni, Y.; MacMillan, D. W. C. J. Am. Chem. Soc. 2006,128, 84.
18. For leading reviews on Brønsted acid, see: (a) Akiyama, T. Chem. Rev. 2007, 107,
5744; (b) Terada, M. Synthesis 2010, 1929; (c) Kampen, D.; Reisinger, C. M.; List,
B. Top. Curr. Chem. 2010, 291, 395; (d) Zamfir, A.; Schenker, S.; Freund, M.;
Tsogoeva, S. B. Org. Biomol. Chem. 2010, 8, 5262; (e) Yu, J.; Shi, F.; Gong, L.-Z. Acc.
Chem. Res. 2011, 44, 1156.
19. (a) Yoshioka, M.; Kawakita, T.; Ohno, M. Tetrahedron Lett. 1989, 30, 1657; (b)
Takahashi, H.; Kawakita, T.; Ohno, M.; Yoshioka, M.; Kobayashi, S. Tetrahedron
1992, 48, 5691; (c) Kull, T.; Peters, R. Adv. Synth. Catal. 2007, 349, 1647.
20. (a) Nakashima, D.; Yamamoto, H. J. Am. Chem. Soc. 2006, 128, 9626; (b) Jiao, P.;
Nakashima, D.; Yamamoto, H. Angew. Chem., Int. Ed. 2008, 47, 2411; (c) Cheon,
C. H.; Yamamoto, H. J. Am. Chem. Soc. 2008, 130, 9246.
4.6.6. threo-5-(Phenylseleno)octan-4-yl benzoate (11f) (Table 6, en-
try 6). Yellow oil; [
a]
20 ꢀ2.7 (c 1.04, CHCl3) (25% ee); IR (film) 1717,
D
1268 cmꢀ1
;
1H NMR (400 MHz, DMSO-d6)
d
7.90 (d, J¼7.2 Hz, 2H),
7.65 (t, J¼7.6 Hz, 1H), 7.62e7.54 (m, 2H), 7.51 (t, J¼7.6 Hz, 2H),
7.35e7.22 (m, 3H), 5.27 (td, J¼6.4, 3.2 Hz, 1H), 3.54e3.43 (m, 1H),
1.90e1.81 (m, 2H), 1.80e1.68 (m, 1H), 1.65e1.18 (m, 5H), 0.85 (t,
J¼7.2 Hz, 3H), 0.79 (t, J¼7.6 Hz, 3H); 13C NMR (100 MHz, DMSO-d6)
d
165.2, 133.3, 133.2, 129.53, 129.51, 129.2, 129.1, 128.7, 127.2, 75.9,
49.2, 34.5, 33.8, 20.6, 18.5, 13.6, 13.5; HRMS calcd for C21H26O2Se
(Mþ): 390.1098; found: 390.1102.
21. For a leading reference on N-phenylselenophthalimide (10), see: Livinghouse, T.;
Back, T. G. e-EROS Encyclopedia of Reagents for Organic Synthesis; John Wiley &
Sons Ltd.: Chichester, UK, 2001.
22. For a leading reference on asymmetric opening of meso-halonium ions, see:
Acknowledgements
€
€
Hennecke, U.; Muller, C. H.; Frohlich, R. Org. Lett. 2011, 13, 860.
23. For a leading reference on chiral phosphoric acid-catalyzed desymmetrization
of meso-aziridines, see: Larson, S. E.; Baso, J. C.; Li, G.; Antilla, J. C. Org. Lett.
2009, 11, 5186.
We gratefully acknowledge the National Basic Research Program
of China (973 program, 2011CB808600), the National Natural

H. Guan et al. / Tetrahedron 68 (2012) 2728e2735
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