Highly enantioselective synthesis of multifunctionalized allylic building blocks via oxazaborolidine-catalyzed borane reduction

Article abstract of DOI:10.1016/j.tet.2005.05.018

A simple and convenient synthesis of optically active alkenyl β-hydroxy sulfides with high enantiomeric excess by CBS-oxazaborolidine- catalyzed borane reduction of the corresponding β-keto sulfides and its application to synthesis of chiral alkenic diols have been established.

Full text of DOI:10.1016/j.tet.2005.05.018

Tetrahedron 61 (2005) 6959–6966
Highly enantioselective synthesis of multifunctionalized allylic
building blocks via oxazaborolidine-catalyzed borane reduction
*
Byung Tae Cho and Sung Hye Shin
Department of Chemistry, Hallym University, Chunchon 200-702, South Korea
Received 25 April 2005; revised 10 May 2005; accepted 11 May 2005
Available online 4 June 2005
Abstract—A simple and convenient synthesis of optically active alkenyl b-hydroxy sulfides with high enantiomeric excess by CBS-
oxazaborolidine-catalyzed borane reduction of the corresponding b-keto sulfides and its application to synthesis of chiral alkenic diols have
been established.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
which could be used as versatile chiral intermediates for
synthesis of biologically active substances.
Optically active allylic alcohols represent an important
structural motif and have attracted synthetic chemists for
their wide range of applications.1,2 Most syntheses of chiral
allylic alcohols are based on kinetic resolution of racemic
allylic alcohols by chemical3 or biological process,2c–e,4
asymmetric hydrogenation,5 or enantioselective reduction6
of vinylic ketones and reductive elimination of 2,3-epoxy7
or O-isopropylidene halides8 and O-isopropylidene acetal
tosylhydrazones.9 On the other hand, non-racemic
b-hydroxy sulfides are widely used as starting materials
for the synthesis of a variety of chiral intermediates in the
synthesis of chiral oxiranes,10a–c aziridines,10d thiiranes,10e
terahydrofurans10f,g and b-hydroxy esters.10h,i Moreover,
they are easily oxidized to b-hydroxy sulfoxides or sulfones,
which serve as extremely useful chiral building blocks for
the synthesis of a variety of chiral organic compounds,11a,b
such as chiral oxiranes,11c,d allylic alcohols,11e,f,12a
lactones,11g,p,12b–e macrolides,11h–l pheromones,11m–o
diols11q and tetrahydrofurans12f because the a-carbon
atom of sulfinyl or sulfonyl groups of the compounds can
be further functionalized by the formation of sulfur-
stabilized carbanions.10b,13 Very recently we reported
highly efficient synthesis of b-hydroxy sulfides with high
enantiomeric purity by CBS-oxazaborolidine-catalyzed
borane reduction.14 Using the same methodology, we
therefore undertook to study the synthesis of optically
active allylic alcohols bearing an adjacent sulfamyl group,
2. Results and discussion
The overall synthetic route is outlined in Scheme 1. The
starting alkenyl b-keto sufides 3 were obtained from
condensation of a-alkenyl esters 1 with methyl p-tolyl
sulfoxide in the presence of base, followed by deoxygena-
tion of product alkenyl b-keto sulfoxides 2. Thus, methyl
p-tolyl sulfoxide was reacted with LDA in THF at K78 8C
for 1 h and the resulting mixture was added to the alkenic
esters 1 in THF at K78 8C using the literature procedure.15
The reactions were maintained at K78 8C for 24 h with
stirring to provide alkenyl b-keto sulfoxides 2 in 55–65%
yield. When 2 was treated with sodium iodide in the
presence of trifluoroacetic anhydride in acetone at 0 8C
according to the known procedure,16 alkenyl b-keto sulfides
3 were obtained in 88–95% yield. Finally, (S)-CBS-
oxazaborolidine (5)-catalyzed asymmetric borane reduction
of 3 using N-ethyl-N-isopropylaniline–borane complex 6 as
borane carrier was carried out.14 To minimize the hydro-
boration of alkenyl group by borane, these reductions were
performed by use of 0.5 equiv of 6 at 0 8C. As shown
Table 1, all the reduction examined afforded the corre-
sponding b-hydroxy sulfides 4 within 10 min in high yields.
Their optical purities were determined by HPLC analysis
using a Chiralcel OD-H or Whelk-O1 chiral column. The
reduction of keto sulfides 3 bearing acyclic (3a and 3b),
exocylic (3c) and endocyclic (3d) alkenyl groups furnished
the corresponding alkenyl b-hydroxy sulfides 4a–d with 90–
95% ee (runs 1–4). For aryl-substituted analogues (3e–h),
the reduction provided very high enantioselection (runs
Keywords: Asymmetric reduction; Oxazaborolidine-catalyzed reduction;
Chiral alkenyl b-hydroxy sulfides; Dianion alkylation; Chiral a,b-
unsaturated diol.
*
Corresponding author. Tel.: C82 33 248 2071; fax: C82 33 251 8491;
e-mail: btcho@hallym.ac.kr
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.05.018

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Scheme 1. (i) LDA (2.1 equiv), MeSOtolyl-p (2.0 equiv), K78 8C, THF, 24 h, 55–65% yield. (ii) NaI (2.0 equiv), (CF3CO)2O (3.0 equiv), 0 8C, acetone, 88–
95% yield. (iii) (S)-5 (0.1 equiv), 6 (0.5 equiv), 0 8C, 93–99% yield.
Table 1. Preparation of optically active allylic b-hydroxy sulfidesa
Run no.
Product 4
Yield (%)b
[a]2D0 in CHCl3
ee (%)
90c
Abs. Config
1
4a
4b
93
K10.05 (c 1.51)
Sd
2
3
95
97
K1.71 (c 1.04)
K0.61 (c 0.8)
97c
90c
Sd
4c
Sd
4
5
6
4d
4e
4f
95
97
98
C6.92 (c 2.01)
K92.33 (c 0.50)
K114.12 (c 0.72)
95c
98f
98c
Se
Se
Sd
7
4g
99
K110.51 (c 1.11)
98e
Sd
8
9
4h
4i
99
95
K64.93 (c 5.51)
K97.32 (c 1.13)
96c
97c
Sd
Sd
a By reduction of 3 with 0.5 equiv of 6 in the presence of 0.1 equiv of 5 in THF at 0 8C.
b Isolated yield.
c Determined by HPLC analysis using a 25 cm Chiralcel OD-H chiral column.
d Determined by HPLC analysis using a 25 cm Whelk O1 chiral column.
e Absolute configuration is unknown, but probably S based on comparison of the elution order of HPLC analysis of 4d and 4e.
By comparison of their known configuration after conversion of 4d and 4e into 7 and 8, respectively.
f

B. T. Cho, S. H. Shin / Tetrahedron 61 (2005) 6959–6966
6961
reacted with 2.5 equiv of sodium acetate in acetic anhydride
at reflux condition to give 1,2-diacetoxy sulfides 8. Without
further purification, these were directly treated with
1.0 equiv of sodium borohydride in 6 N NaOH at room
temperature to give chiral 1,2-diols 9 with O95% ee and 10
with 98% ee in 65 and 60% yields from 4d and 4e,
respectively (Scheme 2).
3. Conclusion
We have established a simple and convenient synthesis of
optically active alkenic b-hydroxy sulfides, which can be
used as versatile chiral intermediates for synthesis of a wide
range of non-racemic compounds including biologically
active substances by employing 5-oxazaborolidine-
catalyzed borane reduction of the corresponding b-keto
sulfides. The reduction provided high enantioselectivity in
all the case of acyclic, endocyclic and exocyclic analogues.
b-Hydroxy sulfides 4d and 4e obtained were successfully
converted into chiral alkenic diols 9 and 10 without
racemization under Pummerer reaction conditions,
respectively.
Figure 1.
5–8). Also, the reduction of a heterocyclic analogue 3i
having 2-furyl group gave 95% ee (run 9). In this reaction,
we found that b-keto sulfides bearing alkenyl group
provided much higher enantioselectivity than the corre-
sponding unhindered aliphatic analogues. For example, the
reduction of 4b containing 1-pentenyl group provided 95%
ee, whereas the case of b-keto sulfide having n-pentyl group
afforded 74% ee.14 These phenomena are attributable that
the alkenyl group behaves as effectively larger than alkyl
group in the oxazaborolidine-catalyzed borane reduction,6
although the reason is unclear so far. All the product
b-hydroxy sulfides 4 obtained are consistently enriched in
the S-enantiomers. The stereochemical course can be
explained by the generally accepted mechanism for
5-catalyzed borane reduction,12f where the b-keto sulfides
3 are attacked by hydride on their Re faces to provide (S)-4
(Fig. 1).17 On the other hand, non-racemic alkenic diols,
such as 918 and 10,19 are frequently used as important
starting materials for synthesis of biologically active
substances. Since b-hydroxy sulfides are easily converted
into diols by Pummerer reaction,11q we examined
preparation of optically active alkenic diols 9 and 10 from
4d and 4e, respectively. When b-hydroxy sulfides 4d and 4e
were treated with 1.1 equiv of m-chloroperbenzoic acid in
dichloromethane at 0 8C, the corresponding sulfoxides 7
were obtained in 96–99% yields. It was subsequently
4. Experimental
4.1. General
All operations with air-sensitive materials were carried out
under a nitrogen atmosphere with oven-dried glassware.
Liquid materials were transferred with a double-ended
needle. The reactions were monitored by TLC using silica
gel plates and the products were purified by flash column
chromatography on silica gel (Merck; 230–400 mesh).
NMR spectra were recorded at 300 MHz for 1H and 75 MHz
for 13C using Me4Si as the internal standard in CDCl3.
Optical rotations were measured with a high resolution
digital polarimeter. Melting points were uncorrected.
Enantiomeric excesses (ees) of the product b-hydroxy
sulfides and diols were determined with a HPLC apparatus
Scheme 2. (i) m-CPBA (1.1 equiv), CH2Cl2, 0 8C. (ii) NaOAc (2.5 equiv), Ac2O, reflux. (iii) NaBH4 (2.5 equiv), 6 N–NaOH–EtOH, rt.

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B. T. Cho, S. H. Shin / Tetrahedron 61 (2005) 6959–6966
fitted with a 25 cm Chiralcel OD-H (Daicel) or Whelk-O1
(Regis) chiral column.
6.03 (s, 1H), 7.29 (d, 2H, JZ7.98 Hz), 7.51–7.54 (m, 2H);
13C NMR (75 MHz, CDCl3) d 21.80, 26.52, 28.29, 29.53,
30.13, 33.95, 39.71, 70.40, 123.01, 124.43, 130.11, 130.26,
142.05, 171.13, 189.95; Anal. Calcd for C17H22O2S: C,
70.31; H, 7.64; S, 11.04. Found: C, 70.34; H, 7.67; S, 11.24.
4.2. Materials
Most of organic compounds utilized in this study were
commercial products of the highest purity. They were
further purified by distillation when necessary. THF was
distilled over sodium benzophenone ketyl and stored in
ampules under nitrogen atmosphere. (S)-CBS reagent 5 and
4.3.5. 1-[(RS)-p-Tolylsulfinyl]-2-(cyclohexen-1-yl)-2-
ethanone 2d. Rf 0.59; oil; 60% yield; IR (neat, cmK1):
3471, 2938, 2859, 1668, 1597, 1454, 1434, 1245, 1086,
1
1041, 1023, 809; H NMR (300 MHz, CDCl3) d 1.61–1.65
N-ethyl-N-isopropylaniline–borane complex
purchased from the Aldrich Chemical Company.
6 were
(m, 8H), 2.40 (s, 3H), 4.06 (d, 1H, JZ13.20 Hz), 4.25 (d,
1H, JZ13.20 Hz), 6.62 (m, 1H), 7.33–7.58 (m, 4H); 13C
NMR (75 MHz, CDCl3) d 21.64, 21.72, 22.12, 24.17, 26.58,
70.35, 130.22, 131.29, 132.54, 137.35, 140.20, 145.76,
190.82; Anal. Calcd for C15H18O2S: C, 68.67; H, 6.92; S,
12.22. Found: C, 68.56; H, 6.95; S, 12.25.
4.3. Preparation of alkenyl b-keto sulfoxides 2
4.3.1. General procedure.15 To a solution of LDA
(5.5 mmol) in THF (15 mL) was added a solution of methyl
p-tolyl sulfoxide (5 mmol) in THF (7.5 mL) dropwise at
K78 8C. After the mixture was stirred at K78 8C for 1 h and
this was slowly added to a solution of a-alkenic ester 1
(5 mmol) in THF (25 mL) at the same temperature via a
syringe with stirring. After 24 h at K78 8C, the reaction
mixture was decomposed with a saturated ammonium
chloride solution (50 mL) and ether (50 mL). Organic
layer was separated and the aqueous solution was extracted
with ether (3!15 mL). The combined extracts were washed
with brine, dried over anhydrous magnesium sulfate, filtered
and evaporated. The crude alkenyl b-hydroxy sulfoxides 2
obtained were further purified by a flash column chroma-
tography on silica gel (230–400 mesh) using ethyl acetate/
hexane (1/1) as the eluent.
4.3.6. (3E)-1-[(RS)-p-Tolylsulfinyl]-4-phenyl-3-buten-2-
one 2e. Rf 0.34; mp 86–88 8C; 60% yield; IR (KBr, cmK1):
3448, 3044, 3025, 2921, 1652, 1627, 1595, 1449, 1268,
1036, 984, 810, 688; 1H NMR (300 MHz, CDCl3) d 2.38 (s,
3H), 4.00 (d, 1H, JZ13.20 Hz), 4.16 (d, 1H, JZ13.20 Hz),
6.69 (d, 1H, JZ16.23 Hz), 7.24–7.41 (m, 5H), 7.46–7.5 (m,
5H); 13C NMR (75 MHz, CDCl3) d 21.80, 67.38, 124.44,
125.98, 128.87, 129.19, 130.25, 131.36, 134.08, 142.39,
145.89, 190.57; Anal. Calcd for C17H16O2S: C, 71.80; H,
5.67; S, 11.28. Found: C, 71.89; H, 5.77; S, 11.42.
4.3.7. (3E)-1-[(RS)-p-Tolylsulfinyl]-4-p-tolyl-3-buten-2-
one 2f. Rf 0.44; mp 82–84 8C; 55% yield; IR (KBr, cmK1):
3264, 3036, 3021, 2917, 1636, 1629, 1597, 1492, 1316,
1
1159, 1037, 992, 806, 700; H NMR (300 MHz, CDCl3) d
4.3.2. 1-[(RS)-p-Tolylsulfinyl]-4-methyl-3-penten-2-one
2a. Rf 0.48; oil; 65% yield; IR (neat, cmK1): 3479, 3461,
2976, 2912, 1674, 1615, 1445, 1381, 1227, 1044, 915, 811;
1H NMR (300 MHz, CDCl3) d 1.82 (d, 3H, JZ1.1 Hz), 2.05
(d, 3H, JZ1.1 Hz), 2.33 (s, 3H), 3.64 (d, 1H, JZ13.20 Hz),
3.83 (d, 1H, JZ13.20 Hz), 6.00 (s, 1H), 7.22 (d, 2H, JZ
8.22 Hz), 7.45 (d, 2H, JZ8.25 Hz); 13C NMR (75 MHz,
CDCl3) d 21.67, 21.79, 28.26, 70.34, 123.64, 124.36,
130.14, 140.37, 142.09, 160.14, 190.30; Anal. Calcd for
C13H16O2S: C, 66.07; H, 6.82; S, 13.57. Found: C, 66.12; H,
6.79; S, 13.54.
2.37 (s, 6H), 3.98 (d, 1H, JZ13.20 Hz), 4.16 (d, 1H, JZ
13.20 Hz), 6.65 (d, 1H, JZ15.95 Hz), 7.16–7.57 (m, 9H);
13C NMR (75 MHz, CDCl3) d 21.80, 21.94, 67.41, 124.45,
125.02, 128.41, 128.92, 129.95, 130.22, 131.35, 142.08,
142.33, 146.01, 190.58; Anal. Calcd for C18H18O2S: C,
72.45; H, 6.08; S, 10.75. Found: C, 2.50; H, 6.16; S, 10.85.
4.3.8. (3E)-1-[(RS)-p-Tolylsulfinyl]-4-(p-chlorophenyl)-3-
buten-2-one 2g. Rf 0.30; mp 116–118 8C; 57% yield; IR
(KBr, cmK1): 3421, 3044, 3026, 2921, 1652, 1627, 1595,
1
1450, 1310, 1296, 1268, 1074, 1037, 984, 810; H NMR
(300 MHz, CDCl3) d 2.38 (s, 3H), 3.98 (d, 1H, JZ
13.20 Hz), 4.11 (d, 1H, JZ13.20 Hz), 6.67 (d, 1H, JZ
15.95 Hz), 7.28–7.55 (m, 9H); 13C NMR (75 MHz, CDCl3)
d 21.79, 67.35, 124.39, 126.36, 128.60, 129.50, 129.97,
130.26, 132.62, 137.35, 142.41, 144.23, 190.36; Anal.
Calcd for C17H15ClO2S: C, 64.04; H, 4.74; S, 10.06. Found:
C, 64.17; H, 4.86; S, 10.01.
4.3.3. (3E)-1-[(RS)-p-Tolylsulfinyl]-3-hepten-2-one 2b. Rf
0.45; oil; 62% yield; IR (neat, cmK1): 3475, 2960, 2931,
2872, 1685, 1617, 1457, 1288, 1085, 1046, 1015, 978, 810;
1H NMR (300 MHz, CDCl3) d 0.92 (t, 3H, JZ7.43 Hz),
1.46 (sextuplet, 2H, JZ7.43 Hz), 2.18 (qd, 2H, JZ7.01,
1.51 Hz), 2.40 (s, 3H), 3.87 (d, 1H, JZ13.20 Hz), 4.08 (d,
1H, JZ13.20 Hz), 6.09 (m, 1H), 6.81 (m, 1H), 7.23 (d, 2H,
JZ7.98 Hz), 7.51–7.55 (m, 2H); 13C NMR (75 MHz,
CDCl3) d 14.01, 21.51, 21.80, 35.01, 66.82, 124.41,
130.19, 130.62, 140.14, 142.27, 151.78, 190.83; Anal.
Calcd for C14H18O2S: C, 67.16; H, 7.25; S, 12.81. Found: C,
67.23; H, 7.28; S, 12.83.
4.3.9. (3E)-1-[(RS)-p-Tolylsulfinyl]-4-(10-naphthyl)-3-
butene-2-one 2h. Rf 0.35; mp 75–77 8C; 65% yield; IR
(KBr, cmK1): 3421, 3335, 3052, 2913, 1644, 1629, 1594,
1493, 1277, 1084, 1041, 978, 813, 732; 1H NMR (300 MHz,
CDCl3) d 2.27 (s, 3H), 4.01 (d, 1H, JZ13.20 Hz), 4.13 (d,
1H, JZ13.20 Hz), 6.69 (d, 1H, JZ15.95 Hz), 7.20–8.31 (m,
12H); 13C NMR (75 MHz, CDCl3) d 21.82, 67.35, 123.39,
124.39, 124.47, 125.60, 125.69, 126.60, 127.42, 128.35,
129.03, 130.29, 131.35, 131.70, 131.81, 133.86, 142.43,
142.95, 190.50; Anal. Calcd for C21H18O2S: C, 75.42; H,
5.42; S, 9.59. Found: C, 75.53; H, 5.54; S, 9.55.
4.3.4. 1-[(RS)-p-Tolylsulfinyl]-3-cycloheptylidenyl-2-
propanone 2c. Rf 0.63; oil; 57% yield; IR (neat, cmK1):
3481,2923, 2853, 1673, 1597, 1444, 1396, 1202, 1088,
1
1041, 1016, 810; H NMR (300 MHz, CDCl3) d 1.50–1.62
(m, 8H), 2.32–2.35 (m, 2H), 2.40 (s, 3H), 2.78–2.82 (m,
2H), 3.72 (d, 1H JZ13.20 Hz), 3.92 (d, 1H, JZ12.93 Hz),

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4.3.10. (3E)-1-[(RS)-p-Tolylsulfinyl]-4-(20-furyl)-3-
buten-2-one 2i. Rf 0.30; mp 107–109 8C; 58% yield; IR
(KBr, cmK1): 3115, 2923, 1614, 1642, 1595, 1445, 1370,
1666, 1634, 1493, 1434, 1277, 1180, 806;1HNMR(300 MHz,
CDCl3) d 1.56–1.64 (m, 4H), 2.20–2.24 (m, 4H), 2.31 (s, 3H),
3.91 (s, 2H) 6.80 (m, 1H), 7.01–7.08 (m, 2H), 7.24–7.27 (m,
2H); 13C NMR (75 MHz, CDCl3) d 21.42, 21.78, 22.22, 23.67,
26.53, 40.97, 129.92, 131.49, 131.85, 137.35, 138.30, 141.71,
195.46;Anal. CalcdforC15H18OS:C,73.13;H, 7.36;S, 13.02.
Found: C, 73.26; H, 7.54; S, 13.06.
1
1265, 1012, 974, 841, 700; H NMR (300 MHz, CDCl3) d
2.38 (s, 3H), 3.93 (d, 1H, JZ13.20 Hz), 4.10 (d, 1H, JZ
13.20 Hz), 6.48 (m, 1H), 6.60 (d, 1H, JZ15.67 Hz), 6.70 (d,
1H, JZ3.58 Hz), 7.25–7.31 (m, 3H), 7.49–7.56 (m, 3H);
13C NMR (75 MHz, CDCl3) d 21.78, 67.74, 113.08, 117.63,
123.11, 124.40, 130.21, 131.42, 141.10, 142.29, 145.90,
150.83, 190.07; Anal. Calcd for C15H14O2S: C, 65.67; H,
5.14; S, 11.69. Found: C, 65.76; H, 5.32; S, 11.74.
4.4.6. (3E)-1-(p-Tolylsulfamyl)-4-phenyl-3-buten-2-one
3e. Rf 0.67; mp 39–41 8C; 92% yield; IR (KBr, cmK1):
3391, 3058, 3025, 2919, 1683, 1608, 1575, 1494, 1331,
1
1204, 1073, 979, 808; H NMR (300 MHz, CDCl3) d 2.30
4.4. Preparation of b-keto sulfides 3 from sulfoxides 2
(s, 3H), 3.79 (s, 2H), 6.95 (d, 1H, JZ15.95 Hz), 7.07 (d, 2H,
JZ7.98 Hz), 7.27–7.58 (m, 8H); 13C NMR (75 MHz,
CDCl3) d 21.44, 44.29, 123.89, 128.65, 129.10, 130.10,
130.83, 131.40, 134.55, 137.66, 144.05, 194.02; Anal.
Calcd for C17H16OS: C, 76.08; H, 6.01; S, 11.95. Found: C,
76.25; H, 6.11; S, 11.90.
4.4.1. General procedure.16 To a suspension of the
sulfoxides 2 (2 mmol) and sodium iodide (4 mmol) in
acetone (20 mL) at 0 8C was added dropwise trifluoroacetic
anhydride (4.8 mmol) at the same temperature with stirring.
After 15 min, the solvent was evaporated under reduced
pressure. To this, a 1:1 saturated solution of sodium sulfite
and sodium bicarbonate was added, extracted with ether
(3!15 mL). The combined organic layer was dried over
anhydrous magnesium sulfate, filtered and evaporated in
vacuo to dryness. The crude alkenyl b-hydroxy sulfides 3
obtained were further purified by a flash column chroma-
tography on silica gel (230–400 mesh) using ethyl acetate/
hexane (1/4) as the eluent.
4.4.7. (3E)-1-(p-Tolylsulfamyl)-4-p-tolyl-3-buten-2-one
3f. Rf 0.56; mp 72–74 8C; 88% yield; IR (KBr, cmK1):
3420, 3021, 2914, 2861, 1678, 1616, 1601, 1566, 1493,
1
1393, 1183, 1161, 1081, 983, 800; H NMR (300 MHz,
CDCl3) d 2.30 (s, 3H), 2.37 (s, 3H), 3.78 (s, 2H), 6.90 (d,
1H, JZ15.95 Hz), 7.05–7.55 (m, 9H); 13C NMR (75 MHz,
CDCl3) d 21.42, 21.88, 44.24, 122.95, 128.67, 129.84,
130.07, 131.35, 131.82, 133.95, 137.58, 141.38, 144.14,
194.13; Anal. Calcd for C18H18OS: C, 76.56; H, 6.42; S,
11.35. Found: C, 76.54; H, 6.46; S, 11.38.
4.4.2. 1-(p-Tolylsulfamyl)-4-methyl-3-penten-2-one 3a.
Rf 0.56; oil; 93% yield; IR (neat, cmK1): 3425, 2975,
2919, 1679, 1666, 1494, 1445, 1391, 1091, 1041, 804; H
1
4.4.8. (3E)-1-(p-Tolylsulfamyl)-4-(p-chlorophenyl)-3-
buten-2-one 3g. Rf 0.47; mp 86–88 8C; 93% yield; IR
(KBr, cmK1): 3453, 2914, 2874, 1678, 1612, 1587, 1489,
NMR (300 MHz, CDCl3) d 1.90 (d, 3H, JZ1.37 Hz), 2.11
(d, 3H, JZ1.10 Hz), 2.30 (s, 3H), 3.59 (s, 2H), 6.26 (m, 1H),
7.06 (d, 2H, JZ8.53 Hz), 7.22–7.25 (m, 2H); 13C NMR
(75 MHz, CDCl3) d 21.29, 21.40, 28.20, 45.99, 122.06,
129.94, 130.64, 131.42, 137.06, 158.05, 194.72; Anal.
Calcd for C13H16OS: C, 70.87; H, 7.32; S, 14.55. Found: C,
70.85; H, 7.41; S, 14.57.
1
1406, 1343, 1077, 1013, 981, 809; H NMR (300 MHz,
CDCl3) d 2.30 (s, 3H), 3.77 (s, 2H), 6.91 (d, 1H, JZ
15.96 Hz), 7.06–7.09 (m, 2H), 7.26–7.52 (m, 7H); 13C NMR
(75 MHz, CDCl3) d 21.43, 44.33, 124.23, 129.39, 129.75,
130.12, 131.40, 133.06, 136.74, 137.74, 142.49, 193.72;
Anal. Calcd for C17H15ClOS: C, 67.43; H, 4.99; S, 10.59.
Found: C, 67.55; H, 5.05; S, 10.63.
4.4.3. (3E)-1-(p-Tolylsulfamyl)-3-hepten-2-one 3b. Rf
0.47; oil; 91% yield; IR (neat, cmK1): 3390, 3367, 2959,
2930, 2871, 1689, 1626, 1490, 1456, 1089, 1041, 806; H
1
4.4.9. (3E)-1-(p-Tolylsulfamyl)-4-(10-naphthyl)-3-buten-
2-one 3h. Rf 0.52; mp 62–64 8C; 92% yield; IR (KBr, cmK1):
3025, 2919, 1683, 1656, 1652, 1576, 1494, 1131, 1073, 807,
NMR (300 MHz, CDCl3) d 0.92 (t, 3H, JZ7.43 Hz), 1.47
(m, 2H), 2.18 (m, 2H), 2.30 (s, 3H), 3.70 (s, 2H), 6.28 (m,
1H), 6.84 (m, 1H), 7.07 (d, 2H, JZ7.70 Hz), 7.24–7.27 (m,
2H); 13C NMR (75 MHz, CDCl3) d 14.04, 21.41, 21.62,
34.85, 43.54, 128.15, 130.01, 131.19, 137.45, 149.22,
194.27; Anal. Calcd for C14H18OS: C, 71.75; H, 7.74; S,
13.68. Found: C, 71.79; H, 7.81; S, 13.71.
1
689; H NMR (300 MHz, CDCl3) d 2.30 (s, 3H), 3.85 (s,
2H), 7.05–7.11 (m, 2H), 7.30–7.52 (m, 6H), 7.75–7.90 (m,
3H), 8.11–8.45 (m, 2H); 13C NMR (75 MHz, CDCl3) d
21.46, 44.40, 123.52, 125.40, 125.61, 126.29, 126.46,
127.15, 128.96, 129.09, 129.92, 130.15, 131.12, 131.43,
131.85, 133.89, 133.97, 140.84, 193.98; Anal. Calcd for
C21H18OS: C, 79.21; H, 5.70; S, 10.07. Found: C, 79.32; H,
5.89; S, 10.13.
4.4.4. 1-(p-Tolylsulfamyl)-3-cycloheptylidenyl-2-propa-
none 3c. Rf 0.70; oil; 95% yield; IR (neat, cmK1): 3019,
2923, 2852, 1672, 1604, 1493, 443, 804; 1H NMR (300 MHz,
CDCl3) d 1.45–1.50 (m, 4H), 1.58–1.63 (m, 4H), 2.30 (s, 3H),
2.34–2.38 (m, 2H), 2.78–2.72 (m, 2H), 3.60 (s, 2H), 6.24 (s,
1H), 7.06 (d, 2H, JZ8.53 Hz), 7.22–7.25 (m, 2H); 13C NMR
(75 MHz, CDCl3) d 21.40, 26.67, 28.46, 29.55, 30.16, 33.44,
39.64, 46.07, 121.57, 129.91, 130.04, 130.72, 130.83, 137.03,
168.77, 194.61; Anal. Calcd for C17H22OS: C, 74.40; H, 8.08;
S, 11.68. Found: C, 74.53; H, 8.29; S, 11.70.
4.4.10. (3E)-1-(p-Tolylsulfamyl)-4-(20-furyl)-3-buten-2-
one 3i. Rf 0.56; oil; 90% yield; IR (neat, cmK1): 3483,
3124, 3021, 2920, 1674, 1606, 1553, 1493, 1389, 1281,
1264, 1082, 1071, 807; 1H NMR (300 MHz, CDCl3) d 2.28
(s, 3H), 3.74 (s, 2H), 6.45 (m, 1H), 6.63 (d, 1H, JZ3.58 Hz),
6.86 (d, 1H, JZ15.40 Hz), 7.06 (d, 2H, JZ8.53 Hz), 7.25–
7.47 (m, 4H); 13C NMR (75 MHz, CDCl3) d 21.43, 44.40,
112.84, 116.45, 121.24, 130.02, 130.06, 130.91, 131.14,
133.86, 137.48, 145.28, 151.25, 193.67; Anal. Calcd for
4.4.5. 1-(p-Tolylsulfamyl)-2-(cyclohexen-1-yl)-2-ethanone
3d. Rf 0.69; oil;92% yield;IR(neat, cmK1):3019, 2933, 2859,

6964
B. T. Cho, S. H. Shin / Tetrahedron 61 (2005) 6959–6966
C15H14O2S: C, 69.74; H, 5.46; S, 12.41. Found: C, 69.77; H,
5.54; S, 12.48.
2.17–2.22 (m, 4H), 2.32 (s, 3H), 2.88 (dd, 1H, JZ13.62,
8.67 Hz), 3.05 (dd, 1H, JZ13.48, 4.13 Hz), 4.38 (m, 1H),
5.17 (m, 1H), 7.08 (d, 2H, JZ7.01 Hz), 7.24–7.23 (m, 2H);
13C NMR (75 MHz, CDCl3) d 21.38, 27.59, 29.09, 29.2,
29.95, 30.61, 38.11, 42.94, 66.37, 125.76, 129.95, 130.70,
131.73, 136.83, 146.35; Anal. Calcd for C17H24OS: C,
73.86; H, 8.75; S, 11.60. Found: C, 73.90; H, 8.89; S, 11.59;
[a]2D0 K0.61 (c 0.8, CHCl3), S; HPLC analysis using a
25 cm Chiralcel OD-H chiral column (iso-PrOH/hexane:
1/9; flow rate: 0.3 mL/min; detector: 254 nm) showed it to
be 90% ee (tR(S) 18.86 min and tR(R) 20.17 min).
4.5. Preparation of optically active alkenyl b-hydroxy
sulfides 4
4.5.1. General procedure. To a solution of 5 (0.2 mmol;
0.2 M, 1.0 mL) in THF was added a solution of N-ethyl-N-
isopropylaniline–borane complex 6 (1.0 mmol; 2.0 M,
0.5 mL) in THF. To this was added slowly 2.5 mL of THF
solution of 3 (2 mmol) over a period of 1.5 h using a syringe
pump at 0 8C. After the addition, the reaction mixture was
stirred for 10 min, quenched cautiously with methanol
(0.5 mL), and stirred for additional 30 min. The solvent was
evaporated under reduced pressure. The crude alkenyl
b-hydroxy sulfides 4 obtained were further purified by a
flash column chromatography on silica gel (230–400 mesh)
using ethyl acetate/hexane (1/4) as the eluent. The
enantiomeric excesses of 4 were determined by HPLC
analysis using a 25 cm Chiralcel OD-H or Whelk-O1 chiral
column. Absolute configurations were assigned by com-
parison of the literature values reported or analogy based on
the elution order of HPLC analysis and/or the sign of the
optical rotation values compared to those of the p-tolyl- or
phenylsulfamyl analogues published.14
4.5.5. (2S)-1-(p-Tolylsulfamyl)-2-(cyclohexen-1-yl)-2-
ethanol 4d. Rf 0.33; oil; 95% yield; IR (neat, cmK1):
3373, 3364, 2921, 2850, 1493, 1445, 1360, 1240, 1091,
1042, 1017, 974, 802; 1H NMR (300 MHz, CDCl3) d 1.07–
1.28 (m, 4H), 1.71–1.91 (m, 4H), 2.31 (s, 3H), 2.98 (dd, 1H,
JZ13.34, 7.56 Hz), 3.05 (dd, 1H, JZ13.48, 3.85 Hz), 3.83
(m, 1H), 4.63 (s, 1H), 7.07 (d, 2H, JZ7.71 Hz), 7.24–7.23
(m, 2H); 13C NMR (75 MHz, CDCl3) d 21.39, 22.80, 22.87,
24.27, 25.31, 41.64, 73.72, 124.42, 129.96, 131.02, 131.61,
136.94, 137.88; Anal. Calcd for C15H20OS: C, 72.53; H,
8.12; S, 12.91. Found: C, 72.66; H, 8.34; S, 11.45; [a]D20
K6.92 (c 2.01, CHCl3), S; HPLC analysis using a 25 cm
Chiralcel OD-H chiral column (iso-PrOH/hexane: 1/9; flow
rate: 0.3 mL/min; detector: 254 nm) showed it to be 95% ee
(tR(S) 21.68 min and tR(R) 23.14 min).
4.5.2. (2S)-1-(p-Tolylsulfamyl)-4-methyl-3-penten-2-ol
4a. Rf 0.33; oil; 93% yield; IR (neat, cmK1): 3395, 3373,
2969, 2919, 2869, 1493, 1376, 1091, 1017, 982, 804; H
1
4.5.6. (2S,3E)-1-(p-Tolylsulfamyl)-4-phenyl-3-buten-2-ol
4e. Rf 0.35; oil; 97% yield; IR (neat, cmK1): 3395, 3373,
3057, 3024, 2960, 2919, 1493, 1448, 1399, 1091, 1017, 966,
805, 750, 692; 1H NMR (300 MHz, CDCl3) d 2.32 (s, 3H),
2.64 (d, 1H, JZ3.03 Hz), 2.97 (dd, 1H, JZ13.62, 8.40 Hz),
3.18 (dd, 1H, JZ13.62, 3.99 Hz), 4.33 (m, 1H), 6.16 (dd,
1H, JZ15.68, 6.33 Hz), 6.60 (d, 1H, JZ15.95 Hz), 7.09–
7.34 (m, 9H); 13C NMR (75 MHz, CDCl3) d 21.43, 43.31,
70.50, 126.72, 127.99, 128.73, 129.84, 130.12, 131.17,
131.42, 131.53, 136.59, 137.34; Anal. Calcd for C17H18OS:
C, 75.51; H, 6.71; S, 11.86. Found: C, 75.57; H, 6.97; S,
11.90; [a]2D0 K92.33 (c 0.50, CHCl3), S; HPLC analysis
using a 25 cm Whelk-O1 chiral column (iso-PrOH/hexane:
1/9; flow rate: 1.0 mL/min; detector: 254 nm) showed it to
be 98% ee (tR(S) 7.21 min and tR(R) 8.78 min).
NMR (300 MHz, CDCl3) d 1.53 (d, 3H, JZ1.1 Hz), 1.64 (d,
3H, JZ1.1 Hz), 2.24 (s, 3H), 2.27 (d, 1H, JZ2.48 Hz), 2.80
(dd, 1H, JZ13.62, 8.66 Hz), 2.97 (dd, 1H, JZ13.48,
4.13 Hz), 4.30 (m, 1H), 5.10 (m, 1H), 7.00–7.23 (m, 4H);
13C NMR (75 MHz, CDCl3) d 18.71, 21.39, 26.12, 42.91,
66.77, 125.68, 129.97, 130.81, 131.61, 136.89; Anal. Calcd
for C13H18OS: C, 70.22; H, 8.16; S, 14.42. Found: C, 70.25;
H, 8.27; S, 14.38; [a]D20 K10.05 (c 1.51, CHCl3), S; HPLC
analysis using a 25 cm Chiralcel OD-H chiral column (iso-
PrOH/hexane: 1/9; flow rate: 1.0 mL/min; detector:
254 nm) showed it to be 90% ee (tR(S) 5.62 min and tR(R)
6.47 min).
4.5.3. (2S, 3E)-1-(p-Tolylsulfamyl)-3-hepten-2-ol 4b. Rf
0.35; oil; 95% yield; IR (neat, cmK1): 3363, 3356, 2957,
2925, 2870, 1493, 1399, 1090, 1025, 1015, 969, 806; H
1
4.5.7. (2S,3E)-1-(p-Tolylsulfamyl)-4-p-tolyl-3-buten-2-ol
4f. Rf 0.37; oil; 98% yield; IR (neat, cmK1): 3405, 3381,
3020, 2919, 1493, 1446, 1410, 1091, 1017, 968, 802; H
NMR (300 MHz, CDCl3) d) d 0.89 (t, 3H, JZ7.43 Hz), 1.38
(m, 2H), 1.99 (m, 2H), 2.31 (s, 3H), 2.43 (d, 1H, JZ
3.03 Hz), 2.88 (dd, 1H, JZ13.48, 8.53 Hz), 3.08 (dd, 1H,
JZ13.62, 3.99 Hz), 4.10 (m, 1H), 5.44 (m, 1H), 5.68 (m,
1H), 7.08–7.10 (m, 2H), 7.23–7.30 (m, 2H); 13C NMR
(75 MHz, CDCl3) d 14.01, 21.37, 22.49, 34.62, 43.31,
70.53, 129.99, 130.57, 131.14, 131.53, 133.51, 137.04;
Anal. Calcd for C14H20OS: C, 71.14; H, 8.53; S, 13.57.
Found: C, 71.17; H, 8.55; S, 13.60; [a]2D0 K1.71 (c 1.04,
CHCl3), S; HPLC analysis using a 25 cm Chiralcel OD-H
chiral column (iso-PrOH/hexane: 1/9; flow rate: 0.3 mL/
min; detector: 254 nm) showed it to be 90% ee (tR(S)
17.69 min and tR(R) 18.74 min).
1
NMR (300 MHz, CDCl3) d 2.32 (s, 6H), 2.59 (d, 1H, JZ
3.03 Hz), 2.97 (dd, 1H, JZ13.75, 8.53 Hz), 3.18 (dd, 1H,
JZ13.75, 4.13 Hz), 4.31 (m, 1H), 6.10 (dd, 1H, JZ15.95,
6.33 Hz), 6.56 (d, 1H, JZ15.68 Hz), 7.07–7.34 (m, 8H);
13C NMR (75 MHz, CDCl3) d 21.40, 21.56, 43.33, 70.63,
126.62, 128.81, 129.42, 130.08, 131.29, 131.36, 131.50,
133.82, 137.26, 137.84; Anal. Calcd for C18H20OS: C,
76.01; H, 7.09; S, 11.27. Found: C, 76.23; H, 7.26; S, 11.35;
[a]2D0 K114.12 (c 0.72, CHCl3), S; HPLC analysis using a
25 cm Chiralcel OD-H chiral column (iso-PrOH/hexane:
1/9; flow rate: 1.0 mL/min; detector: 254 nm) showed it to
be 98% ee (tR(S) 10.10 min and tR(R) 14.80 min).
4.5.4. (2S)-1-(p-Tolylsulfamyl)-3-cycloheptylidenyl-2-
propanol 4c. Rf 0.49; oil; 97% yield; IR (neat, cmK1):
3394, 3355. 2921, 2851, 1493, 1435, 1091, 1042, 1017, 986,
4.5.8. (2S,3E)-1-(p-Tolylsulfamyl)-4-(p-chlorophenyl)-3-
buten-2-ol 4g. Rf 0.34; oil; 98% yield; IR (neat, cmK1):
3452, 3425, 2921, 1495, 1410, 1301, 1148, 1089, 1037,
1
803; H NMR (300 MHz, CDCl3) d 1.47–1.56 (m, 8H),

B. T. Cho, S. H. Shin / Tetrahedron 61 (2005) 6959–6966
6965
1015, 959, 811, 760; 1H NMR (300 MHz, CDCl3) d 2.32 (s,
3H), 2.64 (d, 1H, JZ3.03 Hz), 2.97 (dd, 1H, JZ13.62,
8.40 Hz), 3.17 (dd, 1H, JZ13.75, 4.13 Hz), 4.31 (m, 1H),
6.12 (dd, 1H, JZ15.68, 6.05 Hz), 6.55 (dd, 1H, JZ15.95,
1.38 Hz), 7.08–7.33 (m, 8H); 13C NMR (75 MHz, CDCl3) d
21.40, 43.28, 70.36, 127.90, 128.88, 130.12, 130.20, 130.57,
131.46, 133.60, 135.14, 137.41; Anal. Calcd for
C17H17ClOS: C, 66.98; H, 5.62; S, 11.63. Found: C,
67.15; H, 5.65; S, 11.73; [a]2D0 K110.51 (c 1.11, CHCl3),
S; HPLC analysis using a 25 cm Whelk-O1 chiral column
(iso-PrOH/hexane: 1/9; flow rate: 0.5 mL/min; detector:
254 nm) showed it to be 98% ee (tR(S) 11.91 min and tR(R)
13.57 min).
and passed through silica gel. Crude 1,2-diacetoxy sulfides 8
obtained from the evaporation of the solvent followed by
drying under vacuum were dissolved in ethanol (10 mL). To
this was added NaBH4 (3 mmol) in 6 N NaOH (1 mL) and
stirred for 4 h at room temperature. After the reaction
mixture was extracted with ether (3!10 mL), the combined
extracts are concentrated to give 9 or 10, which was further
purified by a flash column chromatography on silica gel
(230–400 mesh) using ethyl acetate/hexane (1/1) as the
eluent.
4.6.2. (S)-1-(Cyclohexen-1-yl)-1,2-ethanediol 9 from 4d.
Rf 0.17; mp 68–70 8C (lit.18 72–73 8C; 65% yield; IR (KBr,
cmK1): 3277, 3252, 2950, 2915, 2873, 1447, 1078, 1054; 1H
NMR (300 MHz, CDCl3) d 1.55–1.68 (m, 4H), 1.87–2.17
(m, 4H), 3.52–3.63 (m, 2H), 4.08 (m, 1H), 5.75 (m, 1H); 13C
NMR (75 MHz, CDCl3) d 22.82, 22.90, 25.20, 25.27, 65.67,
76.48, 124.21, 136.77; Anal. Calcd for C8H14O2: C, 67.57;
H, 9.92; S, 11.86. Found: C, 67.53; H, 9.95; [a]2D0C28.2 (c
0.50, CHCl3), O95% ee with (S)-configuration based on
[a]D20 K28.1 (c 1.02, CHCl3), O95% ee for (R)-9.17
4.5.9. (2S,3E)-1-(p-Tolylsulfamyl)-4-(1-naphthyl)-3-
buten-2-ol 4h. Rf 0.36; oil; 99% yield; IR (neat, cmK1):
3394, 3374, 3055, 3043, 2918, 1493, 1396, 1091, 1016, 969,
797, 775; 1H NMR (300 MHz, CDCl3) d 2.33 (s, 3H), 2.73
(d, 1H, JZ3.30 Hz), 3.06 (dd, 1H, JZ13.48, 8.25 Hz), 3.25
(dd, 1H, JZ13.62, 4.26 Hz), 4.45 (m, 1H), 6.19 (dd, 1H, JZ
15.68, 6.05 Hz), 7.11 (d, 2H, JZ7.70 Hz), 7.34–8.07 (m,
10H); 13C NMR (75 MHz, CDCl3) d 21.43, 43.37, 70.70,
123.97, 124.14, 125.72, 125.97, 126.24, 128.30, 128.69,
130.15, 131.26, 131.32, 131.47, 133.14, 133.75, 134.41,
137.36; Anal. Calcd for C21H20OS: C, 78.71; H, 6.29; S,
10.01. Found: C, 78.78; H, 6.44; S, 9.90; [a]2D0 K64.93 (c
5.51, CHCl3), S; HPLC analysis using a 25 cm Chiralcel
OD-H chiral column (iso-PrOH/hexane: 1/9; flow rate:
1.0 mL/min; detector: 254 nm) showed it to be 96% ee
(tR(S) 19.01 min and tR(R) 29.81 min).
4.6.3. (2S,3E)-4-Phenyl-1,2-butenediol 8 from 4e. Rf 0.14;
mp 49–51 8C; 60% yield; IR (KBr, cmK1): 3424, 3387,
2948, 2910, 2876, 1447, 1079, 1042; H NMR (300 MHz,
1
CDCl3) d 3.57–3.77 (m, 2H), 4.44 (m, 1H), 6.19 (dd, 1H,
JZ15.95, 6.23 Hz), 6.68 (dd, 1H, JZ15.95, 0.83 Hz), 7.24–
7.39 (m, 5H); 13C NMR (75 MHz, CDCl3) d 66.77, 73.51,
126.72, 127.83, 128.15, 128.82, 133.5, 136.43; Anal. Calcd
for C10H12OS: C, 73.15; H, 7.37. Found: C, 73.09; H, 7.49;
[a]D20C34.1 (c 0.50, CHCl3), S {lit.19 [a]2D6C34.92 (c 0.87,
CHCl3) for (S)-10}; HPLC analysis using a 25 cm Chiralcel
OD-H chiral column (iso-PrOH/hexane: 1/9; flow rate:
0.5 mL/min; detector: 254 nm) showed it to be 98% ee
(tR(S) 16.63 min and tR(R) 19.07 min).
4.5.10. (2S,3E)-1-(p-Tolylsulfamyl)-4-(20-furyl)-3-buten-
2-ol 4i. Rf 0.31; oil; 95% yield; IR (neat, cmK1): 3394, 3373,
2920, 1493, 1398, 1091, 1014, 962, 805, 737; H NMR
1
(300 MHz, CDCl3) d 2.32 (s, 3H), 2.59 (d, 1H, JZ3.30 Hz),
2.93 (dd, 1H, JZ13.75, 8.53 Hz), 3.16 (dd, 1H, JZ13.62,
3.99 Hz), 4.28 (m, 1H), 6.10 (dd, 1H, JZ15.82, 6.05 Hz),
6.21 (d, 1H, JZ3.30 Hz), 6.44 (dd, 1H, JZ15.48, 1.38 Hz),
6.33 (dd, 1H, JZ3.30, 1.65 Hz), 7.07–7.32 (m, 5H); 13C
NMR (75 MHz, CDCl3) d 21.40, 43.30, 69.99, 108.61,
111.50, 119.65, 128.36, 130.08, 131.16, 131.38, 137.31,
142.26, 152.33; Anal. Calcd for C15H16O2S: C, 69.20; H,
6.19; S, 12.32. Found: C, 69.34; H, 6.32; S, 12.08; [a]D20
K97.35 (c 1.13, CHCl3), S; HPLC analysis using a 25 cm
Chiralceli OD-H chiral column (iso-PrOH/hexane: 1/9; flow
rate: 1.0 mL/min; detector: 254 nm) showed it to be 97% ee
(tR(S) 10.01 min and tR(R) 11.37 min).
Acknowledgements
This work was supported by the Research Grant from
Hallym University, Korea
References and notes
4.6. Preparation of alkenyl diols 9 and 10
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(2 mmol) in dichloromethane (10 mL) was added dropwise
a solution of m-chloroperbenzoic acid (2.2 mmol) in
dichloromethane (15 mL) for 10 min at 0 8C. After the
mixture was stirred for 30 min at room temperature, organic
layer was separated, washed with 2 N NaOH (2!10 mL)
and brine (2!10 mL), dried over anhydrous MgSO4,
filtered and concentrated to give 7, which could be used
for the following reaction without further purification. A
stirred mixture of 7 and NaOAc (5 mmol) in acetic
anhydride (6 mL) was heated to reflux for 3 h. After excess
of acetic anhydride and acetic acid were removed under
reduced pressure, the residue was dissolved in ether (10 mL)
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