Diastereoselective hydrolysis of α,γ-substituted γ-sultones in the asymmetric synthesis of γ-hydroxy sulfonates

Article abstract of DOI:10.1055/s-2004-815952

The hydrolysis of enantiopure α,γ-substituted γ-sultones with water under mild conditions leads to α,γ-substituted γ-hydroxy methyl sulfonates in very good yields and excellent diastereo- and enantiomeric excesses (de, ee ≥ 98%). The reaction proceeds via a S _N2 mechanism with inversion of configuration at the attacked γ-carbon atom whose absolute configuration was established by X-ray crystallography.

Full text of DOI:10.1055/s-2004-815952

590
PAPER
Diastereoselective Hydrolysis of , -Substituted -Sultones in the Asymmetric
Synthesis of -Hydroxy Sulfonates
D
iastereoselective
i
H
ydrol
e
ysis of
,
-
Substit
e
uted -Sult
r
ones Enders,* Wacharee Harnying, Gerhard Raabe
Institut für Organische Chemie, Rheinisch-Westfälische Technische Hochschule, Professor-Pirlet-Str. 1, 52074 Aachen, Germany
Fax +49(241)8092127; E-mail: Enders@rwth-aachen.de
Received 22 December 2003
secondary and tertiary -sultones) in 2.8% dioxane lead-
Abstract: The hydrolysis of enantiopure , -substituted -sultones
ing to the conclusion that these sultones were hydrolyzed
with water under mild conditions leads to , -substituted -hydroxy
methyl sulfonates in very good yields and excellent diastereo- and
predominantly by an unimolecular mechanism.7 Mori et
al. demonstrated that the hydrolysis of propanesultone in
H218O in a strong alkaline medium (pH > 12) led to 86%
C–O fission and 14% S–O fission corresponding to uni-
molecular and bimolecular mechanisms, respectively.8
The hydrolysis of sultones can lead to hydroxy alkane-
sulfonates by a substitution or to alkenesulfonates by an
elimination reaction. Nilsson found that the ratio of elim-
ination to substitution products increases by going from
enantiomeric excesses (de, ee 98%). The reaction proceeds via a
SN2 mechanism with inversion of configuration at the attacked
carbon atom whose absolute configuration was established by X-
ray crystallography.
-
Key words: sultones, sulfonates, asymmetric synthesis, hydrolysis,
ring-opening
Derivatives of sulfonic acids are important constituents of primary to secondary and tertiary -sultones.9 Kaiser and
living organisms.1 However, in many cases nothing is Püschel have reported the hydrolysis of long chain tertiary
known about their physiological properties. To get further
-sultones giving 67% yield of -hydroxy sulfonate and
insight into their mode of action a stereoselective access 33% yield of unsaturated products consisting of 30% of
to these derivatives is desirable and compulsory for phys- the 3-alkenesulfonate and only 3% of the 2-isomer.10
iological tests. In our ongoing research concerning the
To the best of our knowledge, neither an asymmetric strat-
chemistry of sultones we have now developed an efficient
egy nor the diastereoselectivity of the hydrolysis of -sul-
diastereo- and enantioselective approach to one class of
tones has been investigated so far.
these derivatives, the title -hydroxy sulfonates. Hitherto,
We have recently reported efficient asymmetric electro-
only a few synthetic routes for the asymmetric synthesis
philic -substitutions of benzylsulfonates bearing 1,2:5,6-
of these interesting compounds have been described.
di-O-isopropylidene- -D-allofuranose as a chiral auxilia-
Traynor et al. reported the facile synthesis of -hydroxy
sulfonates from optically active terpene epoxides by nu-
ry with various alkyl halides and nitroolefins.11 Moreover,
we have extended this methodology using allylic halides
as electrophiles for the diastereo- and enantioselective
synthesis of , -substituted -sultones in good yields.12
cleophilic oxirane opening with sodium sulfite.2 The
asymmetric synthesis of -hydroxy sulfonates by BINAP/
Ru-catalyzed hydogenation of -keto sulfonates has been
described by Noyori, Kitamura et al.3 There have been a
few reports on the synthesis of the marine natural product,
D-cysteinolic acid (2-amino-3-hydroxy-propanesulfonic
acid), either starting from protected -amino acids4 or via
ring-opening of chiral aziridines with sodium bisulfite.5
Our synthetic strategy for -hydroxy sulfonates focused
on the hydrolysis of enantio- and diastereomerically pure
-sultones.
We now wish to describe the successful application of
these enantiopure -sultones 1 (Scheme 1) to the asym-
metric synthesis of -hydroxy sulfonates by hydrolysis
with water under mild conditions, the diastereoselectivity
of this ring-opening and thus the mechanism of the sul-
tone hydrolysis.
Sultones are valuable heterocyclic intermediates which
can react with a variety of nucleophiles cleaving the car-
bon-oxygen bond to introduce an alkylsulfonic acid func-
tionality and they also offer novel possibilities for
stereoselective transformations.6 Several reports have
been devoted to the hydrolysis of aliphatic sultones. Bord-
well et al. have studied the effects of methyl substituents
on the hydrolysis rates of -sultone derivatives bearing ei-
ther no, one or two substituents in the -position (primary,
Scheme 1 Asymmetric synthesis of the enantiopure -sultones 1a–e
SYNTHESIS 2004, No. 4, pp 0590–0594
x
x
.
x
x
.2
0
0
4
Advanced online publication: 03.02.2004
DOI: 10.1055/s-2004-815952; Art ID: Z17503SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Diastereoselective Hydrolysis of , -Substituted -Sultones
591
As shown in Scheme 2, refluxing of diastereo- and enan- diastereoselectivity of the reaction, it would be reasonable
tiomerically pure -sultones 1 in a solution of H2O–ace- to assume that the reaction proceeds via a bimolecular nu-
tone (1:2) for 3 days led to the corresponding sulfonic cleophilic substitution with inversion of configuration at
acids 2. In order to obtain the final product in a more ac- the attacked -position of the -sultones rather than via a
cessible form, the sulfonic acids 2 were directly converted unimolecular reaction, which should result in an
-
into the corresponding methyl sulfonates 3 with diaz- epimeric mixture. In addition, the absolute configuration
omethane. The -hydroxy methyl sulfonates 3 were ob- of (R,S)-3a was determined by X-ray crystallography of
tained in very good yields (88–91%) and excellent the corresponding sodium sulfonate.13–15
diastereo- and enantiomeric excesses (de, ee
98%,
The -hydroxy sodium sulfonate 4a could be obtained by
cleaving the methyl group of (R,S)-3a with NaI in acetone
at room temperature (Scheme 3). The X-ray diffraction
study of compound 4a established unambiguously that the
absolute configuration of the stereogenic center at -posi-
tion is S (Figure 1). The configuration of the -hydroxy
methyl sulfonates 3b and 3c is also expected to be (1R,3S)
based on the assumption of an uniform reaction mecha-
nism operating in all substitutions.
Table 1). The ee values of the products, in the case of
(R,S)-3a and (R)-3d, were determined by HPLC analysis
using a chiral stationary phase by comparison with the
racemate and showed that the ring-opening of these sul-
tones with water under such conditions proceeds without
epimerization at the -position of the sulfonyl group. The
hydrolysis of the secondary -sultones 1a–c gave only the
substitution products 3a–c and no elimination products
could be detected from the crude product. However, a
small amount of unsaturated sulfonate could be observed
from the reactions of tertiary -sultones 1d and 1e.
R2
R3
H2O/acetone
reflux 3 d
O
Scheme 3 Cleavage of -hydroxy methyl sulfonate (R,S)-3a to form
the -hydroxy sodium sulfonate (R,S)-4a
S
R1
O
O
1a-e
R3 R2
HO3S
de ≥ 98%, ee ≥ 98%
OH
R1
CH2N2, Et2O
88-91%
R3 R2
CH3O3S
2
OH
R1
3a-e
de ≥ 98%, ee ≥ 98%
Scheme 2 Hydrolysis of the enantiopure -sultones 1 to form the
corresponding -hydroxy methyl sulfonates 3
The hydrolysis of the epimeric sultones (R,R)-1a and
(R,S)-1a gave one single diastereomer, (R,S)-3a and
(R,R)-3a, respectively, whose 1H NMR spectra apparently
were different from each other. Since both diastereomers
obtained differ from each other and due to the excellent
Figure 1 X-ray crystal structure of (R,S)-4a
Table 1 Hydrolysis of the Enantiopure Sultones 1 Affording the -Hydroxy Methyl Sulfonates 3
3
R1
H
R2
R3
H
Yield (%)
de (%)a
ee (%)b
98
(R,S)-3a
(R,R)-3a
(R,S)-3b
(R,S)-3c
(R)-3d
(R)-3e
Me
H
89
91
90
88
88
89
98
98
98
98
–
H
Me
H
98c
t-Bu
H
Me
Et
98c
H
98c
t-Bu
H
Me
Me
Me
Me
98
–
98c
a Determined by 1H NMR and HPLC.
b Determined by HPLC using a chiral stationary phase.
c Based on the ee values of the enantiopure sultones.
Synthesis 2004, No. 4, 590–594 © Thieme Stuttgart · New York

592
D. Enders et al.
PAPER
Methyl (1R,3R)-3-Hydroxy-1-phenylbutane-1-sulfonate [(R,R)-
3a]
In summary, we have developed a facile asymmetric syn-
thesis of , -substituted -hydroxy sulfonates in very
good yields and excellent diastereo- and enantiomeric ex-
cesses (de, ee 98%) by ring-opening of enantiopure -
sultones with water under mild conditions. The inversion
of configuration at the attacked -position leads to the
conclusion that the reported hydrolysis proceeds via a SN2
mechanism.
According to the general procedure, the solution of the enantiopure
sultone (R,S)-1a (21 mg, 0.1 mmol) in acetone–H2O (10:5 mL) was
refluxed for 3 d. The crude product consisting of only one diastereo-
mer was purified by column chromatography (SiO2, Et2O–n-pen-
tane, 1:1) to give (R,R)-3a as a colorless solid (22 mg, 91%); de
98% (NMR); ee 98% (based on the ee value of the sultone); mp
127 ºC; [ ]D24 –2.7 (c 1.1, CHCl3).
IR (KBr): 3062 (m), 3033 (m), 2997 (m), 2955 (m), 2931 (m), 2896
(m), 1500 (m), 1457 (m), 1349 (s), 1238 (w), 1170 (s), 1143 (s),
1075 (s), 987 (s), 924 (w), 833 (s), 778 (m), 722 (m), 699 (m), 623
(m), 589 (s), 506 (m) cm–1.
1H NMR (300 MHz, CDCl3): = 1.22 (d, J = 6.2 Hz, 3 H, CHCH3),
1.46 (br s, 1 H, OH), 2.33 (m, 2 H, CH2), 3.47 (m, 1 H, CHOH), 3.68
(s, 3 H, SO3CH3), 4.63 (dd, J = 10.9, 4.2 Hz, 1 H, CH2CHSO3CH3),
7.37–7.48 (m, 5 H, ArH).
Preparative column chromatography: Merck silica gel 60, particle
size 0.040–0.063 mm (230–240 mesh, flash). Analytical TLC: silica
gel 60 F254 plates from Merck, Darmstadt. Optical rotation values
were measured on a Perkin–Elmer P241 polarimeter. Microanaly-
ses were obtained with a Vario EL element analyzer. Mass spectra
were acquired on a Finnigan SSQ7000 (CI 100 eV; EI 70 eV) spec-
trometer. IR spectra were taken on a Perkin-Elmer FT/IR 1760. 1H
and 13C NMR spectra were recorded on Gemini 300 or Varian Inova
400 and all measurements were performed with tetramethylsilane as
internal standard. Melting points were determined on a Tottoli melt-
ing point apparatus and are uncorrected.
13C NMR (75 MHz, CDCl3): = 24.4 (CH3), 38.9 (CH2), 56.7
(SO3CH3), 63.8 (CHSO3), 64.2 (CHOH), 129.0, 129.2, 129.7
(ArCH), 131.9 (ArC).
MS (CI, 100 eV, CH4): m/z (%) = 245 (1) [M+ + 1], 183 (1), 163 (2),
149 (6), 131 (11), 123 (5), 105 (100), 91 (1), 77 (7).
Preparation of , -Substituted -Hydroxy Methyl Sulfonates
3a–e; General Procedure
Methyl (1R,3S)-1-(4-tert-Butylphenyl)-3-hydroxybutane-1-sul-
fonate [(R,S)-3b]
The enantiopure sultone 1 (0.25 mmol) was dissolved in a H2O-ac-
etone solution (5:10 mL). The solution was heated at reflux for 3 d
until disappearance of the starting material (TLC monitoring). After
removal of acetone under reduced pressure, EtOH (10 mL) was add-
ed. The resulting colorless ethanolic solution was treated with an
etheral solution of diazomethane until the yellow color persisted.
The solvent was evaporated under reduced pressure and the aqueous
residue was extracted with Et2O. The combined organic layers were
washed with brine and dried with Na2SO4. The solvent was evapo-
rated under reduced pressure and the crude product was purified by
flash column chromatography (SiO2, Et2O–n-pentane) to give the
product 2.
According to the general procedure, the solution of the enantiopure
sultone (R,R)-1b (81 mg, 0.3 mmol) in acetone–H2O (10:5 mL) was
refluxed for 3 d. The crude product consisting of only one diastere-
omer was purified by column chromatography (SiO2, Et2O–n-pen-
tane, 1:1) to give (R,S)-3b as a colorless solid (82 mg, 90%); de
98% (NMR); ee 98% (based on the ee value of the sultone); mp
68 ºC; [ ]D29 +37.4 (c 1.3, CHCl3).
IR (CHCl3): 3291 (m), 2966 (s), 2877 (m), 1517 (m), 1464 (m),
1354 (vs), 1169 (vs), 1089 (m), 994 (vs), 947 (m), 859 (m), 848 (m),
758 (s), 603 (s), 584 (m) cm–1.
1H NMR (400 MHz, CDCl3): = 1.20 (d, J = 6.3 Hz, 3 H, CHCH3),
1.31 [s, 9 H, C(CH3)3], 1.87 (br s, 1 H, OH), 2.18 (ddd, J = 14.6, 8.5,
6.9 Hz, 1 H, CHH), 2.52 (ddd, J = 14.6, 7.4, 4.7 Hz, 1 H, CHH),
3.61 (s, 3 H, SO3CH3), 4.06 (m, 1 H, CHOH), 4.50 (t, J = 7.1 Hz, 1
H, CH2CHSO3CH3), 7.35, 7.40 [each d (AB system), J = 8.5 Hz, 2
H, ArH].
13C NMR (100 MHz, CDCl3): = 23.3 (CH3), 31.2 [C(CH3)3], 34.6
[C(CH3)3], 40.0 (CH2), 56.9 (SO3CH3), 63.4 (CHSO3), 65.1
(CHOH), 125.7, 128.8 (ArCH), 129.9, 152.1 (ArC).
Methyl (1R,3S)-3-Hydroxy-1-phenylbutane-1-sulfonate [(R,S)-
3a]
According to the general procedure, the solution of the enan-
tiopure sultone (R,R)-1a (110 mg, 0.5 mmol) in acetone–H2O (10:5
mL) was refluxed for 3 d. The crude product consisting of only one
diastereomer was purified by column chromatography (SiO2, Et2O–
n-pentane, 1:1) to give (R,S)-3a as a colorless solid (112 mg, 89%);
de
98% (NMR); ee 98% (HPLC, Daicel OD, n-heptane–i-
PrOH, 9:1); mp 63 ºC; [ ]D26 +38.85 (c 1.0, CHCl3).
MS (EI, 70 eV): m/z (%) = 300 (1) [M+], 285 (1), 253 (2), 205 (12),
189 (4), 161 (100), 145 (12), 131 (3), 117 (6), 105 (9), 91 (4), 57
(60).
IR (KBr): 3483 (vs), 3033 (w), 2970 (m), 2931 (m), 1498 (w), 1463
(m), 1405 (m), 1346 (s), 1321 (s), 1323 (w), 1168 (vs), 1129 (m),
1076 (m), 968 (vs), 830 (m), 768 (m), 733 (m), 700 (m), 630 (m),
596 (m) cm–1.
1H NMR (400 MHz, CDCl3): = 1.19 (d, J = 6.3 Hz, 3 H, CHCH3),
1.92 (br s, 1 H, OH), 2.19 (ddd, J = 14.3, 8.5, 6.7 Hz, 1 H, CHH),
2.54 (ddd, J = 14.3, 7.4, 4.7 Hz, 1 H, CHH), 3.60 (s, 3 H, SO3CH3),
4.07 (m, 1 H, CHOH), 4.53 (t, J = 7.1 Hz, 1 H, CH2CHSO3CH3),
7.36–7.46 (m, 5 H, ArH).
13C NMR (100 MHz, CDCl3): = 23.3 (CH3), 39.9 (CH2), 57.0
(SO3CH3), 63.7 (CHSO3), 65.1 (CHOH), 128.8, 129.0, 129.2
(ArCH), 133.2 (ArC).
MS (EI, 70 eV): m/z (%) = 244 (0.2) [M+], 200 (1), 149 (8), 105
(100), 91 (4), 77 (5), 65 (1), 51 (3), 45 (22).
Anal. Calcd for C15H24O4S (300.42): C, 59.97; H, 8.05. Found:
C, 59.57; H, 7.77.
Methyl (1R,3S)-3-Hydroxy-1-phenylpentane-1-sulfonate
[(R,S)-3c]
According to the general procedure, the solution of the enantiopure
sultone (R,R)-1c (36 mg, 0.16 mmol) in acetone–H2O (10:5 mL)
was refluxed for 3 d. The crude product consisting of only one dia-
stereomer was purified by column chromatography (SiO2, Et2O–n-
pentane, 1:1) to give (R,S)-3c as a colorless solid (36 mg, 88%); de
98% (NMR); ee 98% (based on the ee value of the sultone); mp
51 ºC; [ ]D30 +40.2 (c 1.0, CHCl3).
Anal. Calcd for C11H16O4S (244.31): C, 54.08; H, 6.60. Found:
C, 54.21; H, 6.74.
IR (KBr): 3488 (vs), 3062 (w), 3034 (w), 2960 (m), 2931 (m), 1497
(w), 1456 (m), 1411 (m), 1338 (s), 1163 (s), 1114 (m), 1077 (m),
997 (vs), 834 (m), 786 (m), 729 (m), 700 (m), 632 (m), 586 (m)
cm–1.
Synthesis 2004, No. 4, 590–594 © Thieme Stuttgart · New York

PAPER
Diastereoselective Hydrolysis of , -Substituted -Sultones
593
1H NMR (300 MHz, CDCl3): = 0.07 (t, J = 7.4 Hz, 3 H, CH2CH3),
1.43 (m, 2 H, CHCH2CH3), 1.84 (br s, 1 H, OH), 2.11 (ddd,
J = 14.6, 8.9, 6.2 Hz, 1 H, CHH), 2.59 (ddd, J = 14.6, 7.9, 4.2 Hz, 1
H, CHH), 3.59 (s, 3 H, SO3CH3), 3.88 (m, 1 H, CHOH), 4.58 (dd,
J = 7.9, 6.2 Hz, 1 H, CH2CHSO3CH3), 7.36–7.47 (m, 5 H, ArH).
13C NMR (75 MHz, CDCl3): = 9.7 (CH3), 30.2 (CH2CH3), 38.3
(CH2), 57.1 (SO3CH3), 63.8 (CHSO3), 70.4 (CHOH), 128.9, 129.1,
129.4 (ArCH), 133.8 (ArC).
Sodium (1R,3S)-3-Hydroxy-1-phenylbutane-1-sulfonate [(R,S)-
4a]
The -hydroxy methyl sulfonate (R,S)-3a (118 mg, 0.48 mmol) was
dissolved in acetone (20 mL) and NaI (80 mg, 0.53 mmol) was add-
ed. The reaction mixture was allowed to stir at r.t. for 24 h. The sol-
vent was evaporated under reduced pressure and the crude product
was purified by recrystallization from EtOH–Et2O to give (R,S)-4a
as a colorless solid (120 mg, 99%); de, ee 98% (based on the de,
ee value of (R,S)-3a); mp 245 ºC; [ ]D24 +10.6 (c 1.1, MeOH).
MS (EI, 70 eV): m/z (%) = 258 (0.2) [M+], 200 (1), 162 (10), 133
(9), 105 (100), 91 (3), 59 (23).
IR (KBr): 3402 (vs), 3061 (w), 3032 (w), 2972 (m), 1639 (m), 1496
(w), 1455 (m), 1407 (m), 1385 (m), 1295 (m), 1244 (s), 1210 (vs),
1170 (vs), 1129 (m), 1091 (m), 1051 (vs), 948 (m), 825 (m), 751
(m), 703 (s), 672 (m), 587 (m) cm–1.
Anal. Calcd for C12H18O4S (258.34): C, 55.79; H, 7.02. Found:
C, 55.82; H, 7.05.
1H NMR (300 MHz, CD3OD): = 1.16 (d, J = 6.2 Hz, 3 H,
CHCH3), 2.31 (ddd, J = 13.6, 9.4, 5.9 Hz, 1 H, CHH), 2.41 (ddd,
J = 13.6, 7.7, 5.4 Hz, 1 H, CHH), 3.69 (dq, J = 13.6, 6.2 Hz, 1 H,
CHOH), 4.00 (dd, J = 9.4, 5.4 Hz, 1 H, CH2CHSO3), 7.24–7.36 (m,
3 H, ArH), 7.44–7.50 (m, 2 H, ArH).
13C NMR (75 MHz, CD3OD): = 20.6 (CH3), 40.1 (CH2), 62.8
(CHSO3), 64.6 (CHOH), 126.4, 127.2, 128.6 (ArCH), 137.0 (ArC).
Methyl (1R)-1-(4-tert-Butylphenyl)-3-hydroxy-3-methylbutane-
1-sulfonate [(R)-3d]
According to the general procedure, the solution of the enantiopure
sultone (R)-1d (61 mg, 0.2 mmol) in acetone–H2O (10:5 mL) was
refluxed for 3 d. The crude product was purified by column chroma-
tography (SiO2, Et2O–n-pentane, 1:1) to give (R)-3d as a colorless
solid (60 mg, 88%); ee 98% (HPLC, Chiralpak AD, n-heptane/i-
PrOH, 9:1); mp 113 ºC; [ ]D28 +21.6 (c 1.0, CHCl3).
–
MS (ESI): m/z (%) = 229 (100) [C10H13SO4 ].
IR (KBr): 3347 (s), 2966 (s), 2871 (m), 1515 (m), 1464 (m), 1350
(vs), 1269 (m), 1235 (m), 1164 (vs), 980 (vs), 909 (m), 855 (m), 781
(m), 603 (s), 576 (m) cm–1.
Acknowledgment
1H NMR (400 MHz, CDCl3): = 1.03, 1.28 (each s, 3 H, CH3), 1.31
[s, 9 H, C(CH3)3], 1.62 (br s, 1 H, OH), 2.39 (dd, J = 14.6, 9.3 Hz,
1 H, CHH), 2.57 (dd, J = 14.6, 2.5 Hz, 1 H, CHH), 3.64 (s, 3 H,
SO3CH3), 4.57 (dd, J = 9.1, 2.5 Hz, 1 H, CH2CHSO3CH3), 7.40 (s,
4 H, ArH).
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 380, Graduiertenkolleg 440) and the Fonds der Chemischen
Industrie. We thank Degussa AG, BASF AG and Bayer AG for the
donation of chemicals.
13C NMR (100 MHz, CDCl3): = 29.0, 30.7 (CH3), 31.2 [C(CH3)3],
34.6 [C(CH3)3], 42.9 (CH2), 56.9 (SO3CH3), 63.1 (CHSO3), 70.2
(COH), 125.7, 129.2 (ArCH), 130.3, 152.1 (ArC).
MS (EI, 70 eV): m/z (%) = 314 (2) [M+], 296 (1), 281 (1), 219 (3),
203 (6), 185 (1), 161 (100), 145 (11), 131 (2), 117 (4), 105 (2), 91
(2), 59 (50).
References
(1) Kalir, A.; Kalir, H. H. In The Chemistry of Sulfonic Acids,
Esters and their Derivatives; Patai, S.; Rappoport, Z., Eds.;
Wiley: Chichester, New York, 1991, Chap. 18.
(2) Traynor, S. G.; Kane, B. J.; Betkouski, M. F.; Hirschy, L. M.
J. Org. Chem. 1979, 44, 1557.
Anal. Calcd for C16H26O4S (314.45): C, 61.12; H, 8.33. Found:
C, 60.82; H, 8.36.
(3) Kitamura, M.; Yoshimura, M.; Kanda, N.; Noyori, R.
Tetrahedron 1999, 55, 8769.
(4) (a) Higashiura, K.; Morino, H.; Matsuura, H.; Toyomaki, Y.;
Ienaga, K. J. Chem. Soc., Perkin Trans. 1 1989, 1479.
(b) Higashiura, K.; Ienaga, K. J. Org. Chem. 1992, 57, 764.
(5) Xu, J. Tetrahedron: Asymmetry 2002, 13, 1129.
(6) For reviews on sultone chemistry see: (a) Mustafa, A.
Chem. Rev. 1954, 57, 195. (b) Fischer, R. F. Ind. Eng.
Chem. 1964, 56, 41. (c) Roberts, D. W.; Williams, D. L.
Tetrahedron 1987, 43, 1027. (d) Buglass, A. J.; Tillet, J. G.
In The Chemistry of Sulfonic Acids, Esters and Their
Derivatives; Patai, S.; Rappoport, Z., Eds.; Wiley:
Chichester, New York, 1991, Chap. 19. (e) Metz, P. J.
Prakt. Chem. 1998, 340, 1.
Methyl (1R)-3-Hydroxy-3-methyl-1-phenylbutane-1-sulfonate
[(R)-3e]
According to the general procedure, the solution of the enantiopure
sultone (R)-1e (59 mg, 0.25 mmol) in acetone–H2O (10:5 mL) was
refluxed for 3 d. The crude product was purified by column chroma-
tography (SiO2, Et2O–n-pentane, 1:1) to give (R)-3e as a colorless
solid (60 mg, 89%); ee 98% (based on the ee value of the sultone);
mp 71.5 ºC; [ ]D26 +16.8 (c 1.0, CHCl3).
IR (KBr): 3513 (vs), 3035 (w), 2970 (m), 2934 (m), 1498 (m), 1458
(m), 1401 (m), 1342 (vs), 1295 (m), 1233 (s), 1161 (vs), 1084 (m),
983 (vs), 834 (m), 795 (m), 700 (m), 625 (m), 540 (m) cm–1.
(7) Bordwell, F. G.; Osborne, C. E.; Chapman, R. D. J. Am.
Chem. Soc. 1959, 81, 2698.
(8) Mori, A.; Nagayama, M.; Mandai, H. Bull. Chem. Soc. Jpn.
1971, 44, 1669.
1H NMR (300 MHz, CDCl3): = 0.98 (s, 3 H, CH3), 1.27 (s, 3 H,
CH3), 1.65 (br s, 1 H, OH), 2.39 (dd, J = 14.6, 9.4 Hz, 1 H, CHH),
2.58 (dd, J = 14.6, 2.5 Hz, 1 H, CHH), 3.63 (s, 3 H, SO3CH3), 4.61
(dd, J = 9.4, 2.5 Hz, 1 H, CH2CHSO3CH3), 7.36–7.44 (m, 3 H,
ArH), 7.45–7.51 (m, 2 H, ArH).
13C NMR (75 MHz, CDCl3): = 28.9 (CH3), 31.0 (CH3), 42.9
(CH2), 57.1 (SO3CH3), 63.5 (CHSO3), 70.3 (COH), 129.0, 129.1,
129.9 (ArCH), 133.9 (ArC).
(9) Nilsson, T. Ph.D. Thesis; University of Lund: Sweden, 1946.
(10) Kaiser, C.; Püschel, F. Chem. Ber. 1964, 97, 2926.
(11) (a) Enders, D.; Vignola, N.; Berner, O. M. Angew. Chem.
Int. Ed. 2002, 41, 109; Angew. Chem. 2002, 114, 116.
(b) Enders, D.; Berner, O. M.; Vignola, N. Chem. Commun.
2001, 2498. (c) Enders, D.; Berner, O. M.; Vignola, N.;
Harnying, W. Synthesis 2002, 1945.
(12) (a) Enders, D.; Harnying, W.; Vignola, N. Synlett 2002,
1727. (b) Enders, D.; Harnying, W.; Vignola, N. Eur. J. Org.
Chem. 2003, 20, 3939.
MS (EI, 70 eV): m/z (%) = 258 (0.3) [M+], 243 (1), 200 (2), 162 (6),
147 (8), 105 (48), 91 (3), 79 (5), 59 (100).
Anal. Calcd for C12H18O4S (258.34): C, 55.79; H, 7.02. Found:
C, 56.06; H, 7.19.
Synthesis 2004, No. 4, 590–594 © Thieme Stuttgart · New York

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PAPER
(13) X-ray Crystallographic Study of 4a: The compound
(C10H16O5.5SNa: Mr = 279.29) crystallizes in monoclinic
space group C2 (Nr. 5) with cell dimensions of
density of –0.17/0.33 eÅ–3. The absolute configuration has
been determined using Flack’s method and a data set
collected using CuK radiation. Xabs = –0.022(55)15 for the
structure shown in Figure 1. The hydrogen positions have
been calculated in idealized positions. Their Us have been
fixed at 1.5 times U of the relevant heavy atom, and no
hydrogen parameters have been refined. The asymmetric
unit contains 1.5 water molecules which explains deviations
between the crystallographic and chemical formulae and
densities. The crystal structure of 4a has been deposited as
supplementary publication no. CCDC 227543 at the
Cambridge Crystallographic Data Centre. Copies of the data
can be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223-
336033; e-mail: deposit@ccdc.cam.ac.uk, or http//
www.ccdc.cam.ac.uk).
a = 14.019(3), b = 5.6250(11), c = 17.061(3) Å, and
= 110.097(3)º. A cell volume of V = 1263.4(4) Å3 and
Z = 4 result in a calculated density of calcd = 1.468 gcm–3.
16500 reflections have been collected in the mode at
T = 298 K on an Bruker SMART APEX CCD diffractometer
employing MoK -radiation ( = 0.71073 Å). Data collection
covered the range –18
h 18, –7 k 7, and –22 l 22
up to max = 28.29º; absorption correction with SADABS
( = 0.301mm–1). The structure has been solved by direct
methods as implemented in the Xtal3.7 suite of
crystallographic routines14 where GENSIN has been used to
generate the structure-invariant relationships and GENTAN
for the general tangent phasing procedure. 1682 observed
reflections [I>2 (I)] have been included in the final full-
matrix least-squares refinement on F involving 159
parameters and converging at R(Rw) = 0.031 (0.041, w = 1/
(14) Hall, S. R.; du Boulay, D. J.; Olthof-Hazekamp, R. Xtal3.7
System, University of Western Australia, 2000.
(15) Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876.
[
2(F) + 0.0004F2]), S = 1.454, and a residual electron
Synthesis 2004, No. 4, 590–594 © Thieme Stuttgart · New York