Short and practical syntheses of (S)-(+)-3-(p-tolylsulfinyl)furan-2(5H)-one and (S)-(+)-3-(p-tolylsulfinyl)-5,6-dihydropyran-2-one

Article abstract of DOI:10.1055/s-0028-1088008

(S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one and (S)-(+)-3-(p-tolylsulfinyl)- 5,6-dihydropyran-2-one can be synthesized by a new and significantly improved method consisting of Knoevenagel condensation of benzyl (R)-(+)-(p- tolylsulfinyl)acetate with the te

Full text of DOI:10.1055/s-0028-1088008

PAPER
1095
Short and Practical Syntheses of (S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one
and (S)-(+)-3-(p-Tolylsulfinyl)-5,6-dihydropyran-2-one
S
a
ynthesis of Chira
a
l
a
-(
p
-Toly
v
lsulfinyl)
a
,
b
i
-Unsa
t
d
urated
L
actone
s
Cruz Cruz,a Angélica Hernández Linares,a Francisco Yuste,*a M. Rosario Martín,b José Luis García Ruano*b
Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Cd. Universitaria, Coyoacán 04510, Mexico
Fax +52(55)56162217; E-mail: yustef@servidor.unam.mx
b
Departamento de Química Orgánica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain
Fax +34(914)973966; E-mail: joseluis.garcia.ruano@uam.es
Received 7 April 2008; revised 17 December 2008
3-(p-tolylsulfinyl)furan-2(5H)-one (1a; Figure 1) is a
very good Michael acceptor in the highly and predictably
enantiocontrolled conjugate addition of organometallic
reagents,8 a process which has found application in natu-
Abstract: (S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one and (S)-(+)-
3-(p-tolylsulfinyl)-5,6-dihydropyran-2-one can be synthesized by a
new and significantly improved method consisting of Knoevenagel
condensation of benzyl (R)-(+)-(p-tolylsulfinyl)acetate with the
tert-butyldimethylsilyl derivatives of 2-hydroxyacetaldehyde or 3- ral product synthesis.9 The improved dienophilic nature of
hydroxypropanal, followed by subsequent reactions of the resulting
mixtures with hydrogen in the presence of palladium-on-carbon and
ethereal hydrogen chloride.
1a compared to that of furan-2(5H)-one is also seen in its
ready reaction with cyclic and acyclic dienes.10 The sulfi-
nyl group of 1a also strongly influences the course of the
Key words: asymmetric synthesis, chiral auxiliaries, sulfoxides,
a,b-unsaturated lactones, butenolides
reaction with diazoalkanes, in terms of reactivity and con-
trol of both the endo/exo and p-facial selectivities (the lat-
ter being completely inverted in the presence of Lewis
acids).11 The relative influences on p-facial selectivity of
a C3-sulfinyl group and C5 chirality on the course of the
reactions with cyclopentadiene (predominant role of C5)12
and diazoalkanes (predominant role of the sulfinyl
group)13 has been studied with both C5 epimers of 5-
ethoxy-3-(p-tolylsulfinyl)furan-2(5H)-ones.
Enantiomerically pure a,b-unsaturated lactones are versa-
tile building blocks for the construction of a wide range of
naturally occurring and/or biologically active molecules.
In particular, butenolides constitute the central skeleton of
several naturally occurring compounds that show interest-
ing physiological activities. The majority of the applica-
tions of these entities in asymmetric synthesis has
involved 5-alkoxy- or 5-(hydroxyalkyl)furan-2(5H)-
ones,1 where the chiral center at C5, adjacent to the C–C
double bond of the lactone ring, efficiently controls the
stereoselectivity of intermolecular cycloadditions (1,3-di-
polar-,2 Diels–Alder-,3 and [2+2] photocycloadditions4)
and Michael reactions.5 The incorporation of chiral cen-
ters at C3 or C4 has been studied much less, despite the
possibility that they might exert a similar degree of con-
trol on the stereoselectivity of certain types of reactions.
To the best of our knowledge, only the sulfinyl group has
been used as chiral auxiliary at the double bond of furan-
2(5H)-ones. Only two papers concerning the behavior of
4-sulfinylfuran-2(5H)-ones in Diels–Alder6 and 1,3-dipo-
lar reactions with diazoalkanes have appeared.7 This may
well be because of the formation of mixtures in these re-
actions, where the sulfinyl group, the carbonyl moiety,
and the chiral center at C5 compete in controlling the
endo/exo and p-facial selectivities.
O
S
O
S
O
O
Tol
O
Tol
O
1b
1a
Figure 1
The known synthetic utility of 3-(p-tolylsulfinyl)furan-
2(5H)-ones as building blocks (as discussed above) con-
trasts with the smaller number of publications dealing
with the use of butenolide 1a in asymmetric synthesis.
Pentenolide (S)-1b (Figure 1), has been used even less,14
although it is expected to exhibit reactivity features simi-
lar to those of 1a. The principal reason for the modest
number of applications reported for 1a and 1b in asym-
metric synthesis is that there have been no efficient syn-
thetic procedures available for these entities. The three
known methods for the synthesis of optically pure 1a have
been described by Posner (seven steps, 13% overall
yield),8a our group (five steps, 27% overall yield),10 and
Holton (four steps, ca. 24% overall yield).15,16 Only one
synthesis of enantiopure 1b has been described to date
(six steps, 17% overall yield).8b,17
In contrast, the incorporation of a sulfinyl group at C3 of
the furan-2(5H)-one system significantly augments its
ability to function as a dienophile, dipolarophile, or
Michael acceptor, and therefore such systems have been
used in many asymmetric transformations. Thus, (S)-(+)-
In our experience, the main problem with the reported
syntheses of 1a is associated with the difficult reproduc-
ibility of the yields in the last, and key, step. In this step,
enantiopure 3-(p-tolylsulfinyl)prop-2-en-1-ol,8a,10 or its
SYNTHESIS 2009, No. 7, pp 1095–1098
Advanced online publication: 06.03.2009
DOI: 10.1055/s-0028-1088008; Art ID: P05008SS
x
x
.
x
x
.2
0
0
9
© Georg Thieme Verlag Stuttgart · New York

1096
D. Cruz Cruz et al.
PAPER
trimethylsiloxy derivative,15 is carboxylated a to the sulfi- a palladium-on-carbon to substrate ratio of 3:1. When
nyl group, and the mixture thus obtained, containing a these conditions were used for three millimoles of com-
mixture of E- and Z-olefinic isomers, is subjected to the pounds 3, the conversions were low. The temperature and
cyclization conditions. We chose to avoid the problem of the reaction time were increased over several trials, but re-
the olefin stereochemistry by introducing the double bond sulted in no improvement. The use of a 1:1 mixture of pal-
after the formation of the cyclic system. Our results are ladium-on-carbon and formic acid in methanol resulted
described below.
only in deprotection of the silyl ether, whereas in the pres-
ence of Raney nickel desulfinylation was also observed.
Finally, the problem was solved by using the initial condi-
tions but increasing the pressure of hydrogen to three
atmospheres. Under these conditions, the complete disap-
pearance of 3a or 3b was observed after 20 hours, and the
yields were only slightly lower than those obtained on the
one-millimole scale. When these conditions were applied
to eight millimoles of 3b, the isolated yield was 42%,
whereas five millimoles of 3a provided a 49% yield, both
after 20 hours of reaction.
Knoevenagel condensation of benzyl (R)-(+)-(p-tolyl-
sulfinyl)acetate (2)18 with commercially available 2-(tert-
butyldimethylsiloxy)acetaldehyde, in the presence of lith-
ium diisopropylamide at –78 °C, gave a mixture of the
four possible diastereomers of 3a (90% combined yield)
(Scheme 1). Although these compounds could be separat-
ed chromatographically and were fully characterized, this
separation is not necessary for synthetic purposes. Hydro-
genolysis of this mixture, by use of 10% palladium-on-
carbon, and subsequent treatment of the resulting mixture
of carboxylic acids with ethereal hydrogen chloride gave In conclusion, butenolide 1a and pentenolide 1b could be
the unsaturated lactone 1a directly in 68% isolated yield synthesized from benzyl (R)-(+)-(p-tolylsulfinyl)acetate
(Scheme 1). The hydrogen chloride treatment thus pro- in procedures that are simpler, shorter, and higher-
moted three consecutive steps, namely desilylation, cy- yielding than those reported previously.20
clization, and dehydration. It is important to note that 1a
decomposes on attempted purification by chromatogra-
All moisture-sensitive reactions were carried out in flame-dried
phy on silica gel.19 It therefore must be purified by crys-
glassware under argon atmosphere. Reactions were monitored by
tallization.
TLC on silica gel. Flash chromatography was performed on silica
gel 60 (230–400 mesh ASTM). Melting points of samples in open
capillary tubes were determined with a Culatti melting point appa-
ratus and are uncorrected. The optical rotations were measured at
r.t. on a Perkin-Elmer 343 polarimeter (concentration in g/100 mL).
The IR spectra were recorded with a FT-IR Bruker Tensor 27 spec-
trophotometer. The NMR spectra were determined on a Varian Uni-
ty 300 or Jeol Eclipse 300 NMR spectrometer. Mass spectra were
obtained with a Jeol JMS-SX 102A or JMS-AX 505 HA mass spec-
trometer.
O
S
O
O
O
LDA, THF, –78 °C
TBDMSO
OBn
OTBDMS
Tol
S
OBn
Tol
CHO
n
n
HO
3a n = 1
3b n = 2
2
O
O
1. 10% Pd/C
EtOAc, r.t.
S
Benzyl Esters 3; General Procedure
Tol
O
2. HCl, Et2O
CH2Cl2, r.t.
A soln of benzyl (R)-(+)-(p-tolylsulfinyl)acetate (2; 2.88 g, 10
mmol) in THF (20 mL) was added dropwise to a soln of LDA (10
mmol) in THF (20 mL) at –78 °C. The mixture was stirred at –78
°C for 0.5 h. Then a soln of 2-(tert-butyldimethylsiloxy)acetalde-
hyde (for 3a) or 3-(tert-butyldimethylsiloxy)propanal (for 3b) (30
mmol, 3 equiv) in THF (20 mL) was added, and the resulting mix-
ture was stirred at –78 °C for 2.5 h. The reaction mixture was
quenched with sat. aq NH4Cl (50 mL) and extracted with CH2Cl2
(3 × 30 mL). The organic layers were dried (Na2SO4) and concen-
trated. The residue was analyzed by 1H NMR spectroscopy and pu-
rified by flash chromatography as indicated for each case below.
n
1a n = 1
1b n = 2
Scheme 1
When this sequence was repeated with 3-(tert-butyldi-
methylsiloxy)propanal, the mixture of the four diastereo-
mers of 3b was obtained in 82% combined yield. This
stereoisomeric mixture, when subjected to the two-step
process described above for 3a, produced compound 1b in Benzyl (RS)-4-(tert-Butyldimethylsiloxy)-3-hydroxy-2-(p-tolyl-
sulfinyl)butanoate (3a)
48% yield (Scheme 1).
Compound 3a was obtained as a mixture of the four possible dia-
stereomers. The product was purified by flash chromatography (sil-
ica gel, hexane–EtOAc, 8:2).
Because compounds 1a and 1b are mainly useful as start-
ing materials, we then tried to scale up the procedure. The
Knoevenagel condensation (step 1) could be performed
on a larger scale (up to 10 mmol) with similar or even bet-
ter yields (90% for 3a and 85% for 3b). In contrast, the ef-
ficiency of the hydrogenolysis of compounds 3a and 3b is
highly dependent on the reaction conditions. The yields
reported above are obtained for reactions run over four
hours at room temperature, under one atmosphere of hy-
drogen, starting with one millimole of 3a or 3b, and with
Yield: 4.20 g (90%).
IR (film): 3373, 2930, 2857, 1731, 1256, 839 cm–1.
First Less-Polar Diastereomer
1H NMR (300 MHz, CDCl3): d = 0.01 (s, 3 H), 0.03 (s, 3 H), 0.86
(s, 9 H), 2.38 (s, 3 H), 3.68 (dd, J = 4.5, 10.5 Hz, 1 H), 3.74 (dd,
J = 4.5, 10.5 Hz, 1 H), 3.81 (br s, 1 H), 3.92 (d, J = 8.7 Hz, 1 H),
4.33–4.39 (m, 1 H), 4.92 (s, 2 H), 7.14–7.37 (m, 7 H), 7.50 (half of
an AA¢BB¢ system, 2 H).
Synthesis 2009, No. 7, 1095–1098 © Thieme Stuttgart · New York

PAPER
Synthesis of Chiral a-(p-Tolylsulfinyl) a,b-Unsaturated Lactones
1097
13C NMR (75 MHz, CDCl3): d = –5.6, –5.5, 18.3, 21.5, 25.8, 65.0,
67.2, 71.4, 73.3, 125.3, 128.4 (3 C), 129.8, 134.7, 138.0, 142.7,
165.5.
(m, 2 H), 2.38 (s, 6 H), 3.58 (d, J = 3.9 Hz, 1 H), 3.77–3.90 (m, 5
H), 4.53 (dt, J = 3.0, 7.8 Hz, 1 H), 4.65–4.69 (m, 1 H), 4.96 (s, 2 H),
5.00 (AB system, 2 H), 7.14–7.38 (m, 14 H), 7.51 (half of an
AA¢BB¢ system, 2 H), and 7.51 (half of an AA¢BB¢ system, 2 H).
13C NMR (75 MHz, CDCl3): d = –5.5 (2 C), –5.4 (2 C), 18.1, 18.2,
21.5, 25.8 (2 C), 36.4, 37.0, 60.9, 61.1, 67.2, 67.3, 68.3, 75.9, 76.1,
125.2 (2 C), 128.4 (2 C), 128.5 (2 C) 128.5 (2 C), 129.8, 129.9,
134.7 (2 C), 138.2, 138.7, 142.5, 142.7, 165.8, 166.6.
MS (EI): m/z (%) = 477 (5) [M + 1]+, 419 (15), 139 (69), 91 (100),
75 (35).
HRMS–FAB: m/z [M + 1]+ calcd for C25H37O5SSi: 477.2131;
found: 477.2126.
Second Less-Polar Diastereomer
1H NMR (300 MHz, CDCl3): d = –0.01 (s, 3 H), 0.00 (s, 3 H), 0.82
(s, 9 H), 2.37 (s, 3 H), 3.63 (d, J = 7.5 Hz, 1 H), 3.67 (d, J = 3.3 Hz,
1 H), 3.74 (dd, J = 4.5, 10.5 Hz, 1 H), 3.83 (dd, J = 5.7, 10.5 Hz, 1
H), 4.43–4.50 (m, 1 H), 4.96 (s, 2 H), 7.10–7.33 (m, 7 H), 7.50 (half
of an AA¢BB¢ system, 2 H).
13C NMR (75 MHz, CDCl3): d = –5.6, –5.5, 18.2, 21.4, 25.7, 64.9,
67.4, 69.2, 73.3, 125.0, 128.3, 128.5, 129.9, 134.5, 138.6, 142.5,
166.8.
Lactones 1; General Procedure
Third Less-Polar Diastereomer
1H NMR (300 MHz, CDCl3): d = 0.04 (s, 3 H), 0.04 (s, 3 H), 0.87
(s, 9 H), 2.38 (s, 3 H), 3.76 (dd, J = 4.5, 10.8 Hz, 1 H), 3.77 (d,
J = 6.0 Hz, 1 H), 3.91 (dd, J = 4.2, 10.5 Hz, 1 H), 4.14–4.22 (m, 1
H), 5.04 (AB system, 2 H), 7.19–7.33 (m, 7 H), 7.50 (half of an
AA¢BB¢ system, 2 H).
A mixture of 10% Pd/C (7.16 g for 3a or 11.5 g for 3b) was added
to a soln of 3 [3a (2.31 g, 5 mmol) or 3b (3.80 g, 8 mmol)] in EtOAc
(250 mL for 3a or 400 mL for 3b). The reaction mixture was vigor-
ously stirred under H2 (3 atm) at 25 °C for 20 h, and was then fil-
tered through Celite and washed with EtOH (5 × 100 mL). The
combined filtrate and washings were concentrated under vacuum.
The residue was diluted with CH2Cl2 (25 mL), treated with a sat.
soln of HCl in Et2O (1.7 mL for 3a or 2.5 mL for 3b), and stirred at
25 °C for 1 h. The volatiles were removed and the residue was pu-
rified as indicated below for each case.
13C NMR (75 MHz, CDCl3): d = –5.5 (2 C), 18.2, 21.5, 25.8, 64.4,
67.4, 69.6, 70.7, 124.6, 128.3 (2 C), 128.4, 129.9, 134.8, 138.0,
142.2, 166.3.
More-Polar Diastereomer
1H NMR (300 MHz, CDCl3): d = –0.01 (s, 3 H), 0.02 (s, 3 H), 0.85
(s, 9 H), 2.36 (s, 3 H), 3.32 (d, J = 5.4 Hz, 1 H), 3.62 (dd, J = 4.2,
10.8 Hz, 1 H), 3.74 (d, J = 8.7 Hz, 1 H), 3.79 (dd, J = 3.9, 10.5 Hz,
1 H), 4.44–4.51 (m, 1 H), 4.74 and 4.91 (AB system, 2 H), 7.08–
7.13 (m, 2 H), 7.28–7.31 (m, 3 H), 7.23 and 7.43 (AA¢BB¢ system,
4 H).
Alternative with the use of 1 mmol 3a or 3b: A mixture of 10%
Pd/C (1.5 g) was added to a soln of 3 (1 mmol) in EtOAc (50 mL).
The reaction mixture was vigorously stirred under H2 (1 atm) at 25
°C for 4 h, and then filtered through Celite and washed with EtOH
(5 × 20 mL). The combined filtrate and washings were concentrated
under vacuum. The residue was diluted with CH2Cl2 (5 mL), treated
with a sat. soln of HCl in Et2O (0.5 mL), and stirred at 25 °C for 20
min. The volatiles were removed and the residue was purified as in-
dicated below for each case.
13C NMR (75 MHz, CDCl3): d = –5.6, –5.5, 18.2, 21.4, 25.8, 64.8,
67.0, 69.0, 70.8, 124.4, 128.4 (2 C), 128.4, 129.7, 134.7, 137.9,
141.7, 164.6.
MS (EI): m/z (%) = 463 (4) [M + 1]+, 405 (72), 139 (65), 91 (100).
(S)-(+)-3-(p-Tolylsulfinyl)furan-2(5H)-one (1a)
The residual oil was diluted with CHCl3 and stirred at 25 °C for 6 d.
Then the solvent was evaporated and the residue was crystallized
from Et2O; yield: 0.543 g (49%).
Anal. Calcd for C24H34O5SSi: C, 62.30; H, 7.41; S, 6.93. Found: C,
62.36; H, 7.38; S, 6.85.
Benzyl (RS)-5-(tert-Butyldimethylsiloxy)-3-hydroxy-2-(p-tolyl-
sulfinyl)pentanoate (3b)
When 1a was obtained from 1 mmol of 3a, it was purified by crys-
tallization from EtOAc–hexane; yield: 0.151 g (68%).
Compound 3b was obtained as a mixture of the four possible dia-
stereomers. Purification of the product by flash chromatography
(silica gel, hexane–EtOAc, 8:2) gave two mixtures, each containing
two inseparable diastereomers.
Mp 121–125 °C (Lit.8a,10 121–125 °C); [a]D20 +252.9 (c 1.3, CHCl3)
[Lit.8a,10 [a]D20 +244 (c 1.3, CHCl3)].
IR (film): 3013, 1772, 1340, 1144, 1043, 997 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.40 (s, 3 H), 4.90 (dd, J = 1.7,
18.3 Hz, 1 H), 5.03 (dd, J = 1.7, 18.3 Hz, 1 H), 7.33, 7.69 (AA¢BB¢
system, 4 H), 8.05 (t, J = 1.7 Hz, 1 H).
Yield: 4.05 g (85%).
IR (film): 3382, 2930, 2857, 1730, 1255, 1088, 837 cm–1.
13C NMR (75 MHz, CDCl3): d = 21.5, 71.3, 125.1, 130.2, 137.7,
Less-Polar Mixture of Two Diastereomers
1H NMR (300 MHz, CDCl3): d = 0.00 (s, 3 H), 0.03 (s, 3 H), 0.07
(s, 3 H), 0.08 (s, 3 H), 0.84 (s, 9 H), 0.89 (s, 9 H), 1.65–2.00 (m, 4
H), 2.37 (s, 3 H), 2.38 (s, 3 H), 3.59 (d, J = 6.3 Hz, 1 H), 3.60 (d,
J = 9.3 Hz, 1 H), 3.72–3.84 (m, 2 H), 3.88 (dd, J = 4.8, 6.3 Hz, 2 H),
4.25 (br s, 1 H), 4.36 (br s, 1 H), 4.66 (dt, J = 2.4, 8.7 Hz, 2 H), 4.71
and 4.92 (AB system, 2 H), 5.03 and 5.14 (AB system, 2 H), 7.07–
7.33 (m, 14 H), 7.42 (half of an AA¢BB¢ system, 2 H) and 7.53 (half
of an AA¢BB¢ system, 2 H).
141.5, 143.0, 151.2, 167.0.
MS (EI): m/z (%) = 222 (50) [M+], 174 (100), 139 (61), 117 (55), 91
(38), 65 (25).
(S)-(+)-3-(p-Tolylsulfinyl)-5,6-dihydropyran-2-one (1b)
The residual oil was purified by flash chromatography (silica gel,
hexane–EtOAc, 2:8); this gave 1b as white crystals; yield: 0.793 g
(42%); ee >98%.21
13C NMR (75 MHz, CDCl3): d = –5.6 (2 C), –5.6 (2 C), 18.1 (2 C),
21.4 (2 C), 25.8 (2 C), 36.1 (2 C), 61.0, 62.1, 67.0, 67.4, 68.8 (2 C),
74.1, 74.8, 124.3, 124.7, 128.3 (2 C) 128.3 (2 C), 128.4 (2 C), 129.7,
129.9, 134.7, 134.9, 138.1 (2 C), 141.6, 142.1, 164.6 (2 C).
When 1b was obtained from 1 mmol of 3b, the crude product was
purified by chromatography (silica gel, EtOAc); this gave 1b as
white crystals; yield: 0.113 g (48%).
20
Mp 81–82 °C (Lit.8b 93–94 °C); [a]D +254.4 (c 0.27, CHCl3)
[Lit.8b [a]D20 +212.78 (c 0.27, CHCl3)].
More-Polar Mixture of Two Diastereomers
IR (KBr): 3048, 2966, 2918, 1708, 1086, 1049 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.04 (s, 6 H), 0.06 (s, 3 H), 0.07
(s, 3 H), 0.87 (s, 9 H), 0.90 (s, 9 H), 1.76–1.81 (m, 2 H), 1.84–1.92
Synthesis 2009, No. 7, 1095–1098 © Thieme Stuttgart · New York

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D. Cruz Cruz et al.
PAPER
1H NMR (300 MHz, CDCl3): d = 2.38 (s, 3 H), 2.63 (qd, J = 4.8,
18.9 Hz, 1 H), 2.73–2.86 (m, 1 H), 4.28 (ddd, J = 4.8, 9.9, 11.1 Hz,
1 H), 4.42–4.50 (m, 1 H), 7.28, 7.65 (AA¢BB¢ system, 4 H), 7.69
(ddd, J = 1.5, 3.5, 5.5 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 21.4, 24.8, 66.2, 125.5, 129.9,
139.3, 139.7, 142.3, 143.3, 160.1.
(4) Rustullet, A.; Alibés, R.; de March, P.; Figueredo, M.; Font,
J. Org. Lett. 2007, 9, 2827; and references cited therein.
(5) (a) Felzmann, W.; Arion, V. B.; Mieousset, J.-L.; Mulzer, J.
Org. Lett. 2006, 8, 3849. (b) He, L.; Liu, Y.; Rosso, G. B.;
Pilli, R. A. Tetrahedron Lett. 2006, 47, 185.
(6) García Ruano, J. L.; Bercial, F.; Fraile, A.; Martín Castro, A.
M.; Martín, M. R. Tetrahedron: Asymmetry 2000, 11, 4737.
(7) García Ruano, J. L.; Bercial González, G.; Martín Castro, A.
M.; Martín, M. R. Tetrahedron: Asymmetry 2002, 13, 1993.
(8) (a) Posner, G. H.; Kogan, T. P.; Haines, S. R.; Frye, L. L.
Tetrahedron Lett. 1984, 25, 2627. (b) Posner, G. H.;
Weitzberg, M.; Hamill, T. G.; Aisrvatham, E.; Cun-heng, H.;
Clardy, J. Tetrahedron 1986, 42, 2919.
MS (EI): m/z (%) = 236 (100) [M+], 188 (30), 139 (41), 123 (17),
107 (21), 91 (19).
Acknowledgment
We thank M. I. Chávez, E. García-Ríos, E. Huerta, R. Patiño, M. A.
Peña, J. Pérez, B. Quiroz, H. Ríos, L. Velasco, and M. N. Zavala for
their technical assistance. D.C.C. thanks Consejo Nacional de Cien-
cia y Tecnología (CONACYT-México) for a predoctoral fel-
lowship. We also thank Dr. J. M. Muchowski for the critical
reviewing of the manuscript.
(9) (a) Posner, G. H. Acc. Chem. Res. 1987, 20, 72. (b) Posner,
G. H.; Weitzberg, M.; Sup, S. S. Synth. Commun. 1987, 17,
611. (c) See refs. 8a and 8b. (d) Holton, R. A.; Kennedy, R.
M.; Kim, H.-B.; Krafft, M. E. J. Am. Chem. Soc. 1987, 109,
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(10) Carretero, J. C.; García Ruano, J. L.; Martín Cabrejas, L. M.
Tetrahedron 1997, 53, 14115.
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A.; Martín, M. R.; Tito, A. J. Org. Chem. 2005, 70, 8942.
(12) Carretero, J. C.; García Ruano, J. L.; Lorente, A.; Yuste, F.
Tetrahedron: Asymmetry 1993, 4, 177.
(13) García Ruano, J. L.; Fraile, A.; González, G.; Martín, M. R.;
Clemente, F. R.; Gordillo, R. J. Org. Chem. 2003, 68, 6522.
(14) (a) Posner, G. H.; Hamill, T. G. J. Org. Chem. 1988, 53,
6031. (b) Posner, G. H.; Haces, A.; Harrison, W.; Kinter, C.
M. J. Org. Chem. 1987, 52, 4836.
(15) Holton, R. A.; Kim, H.-B. Tetrahedron Lett. 1986, 27, 2191.
(16) One of the starting products is not commercially available
and needs to be prepared by ozonolysis of suitable
precursors.
(17) The synthesis of ( )-1b (three steps and 25% overall yield)
has also been reported; see ref. 8b.
(18) Alonso, I.; Carretero, J. C.; García Ruano, J. L. J. Org.
Chem. 1994, 59, 1499.
(19) 5-Hydroxyfuran-2(5H)-one was the only product we could
identify when the crude reaction mixture containing 1a was
purified by column chromatography.
(20) Starting from menthyl p-toluenesulfinate (commercially
available in the two possible configurations at sulfur),
compounds 1a and 1b are obtained in 41% (30% on 5 mmol
scale) and 26% (24% on 8 mmol scale) overall yield,
respectively.
(21) The ee of (+)-1b was determined from the well-separated p-
tolyl signals in the 1H NMR spectrum by use of tris[3-(hep-
tafluoropropylhydroxymethylene)-(+)-camphorato]ytter-
bium(III) as chiral shift reagent.
References
(1) (a) Tatsuta, K.; Suzuki, Y.; Furuyama, A.; Ikegami, H.
Tetrahedron Lett. 2006, 47, 3595. (b) Zhang, X.; Huang,
H.-H.; Chen, Q.-H. J. Asian Nat. Prod. Res. 2005, 7, 711.
(c) Ishibashi, F.; Park, S.; Kusano, T.; Kuwano, K. Biosci.,
Biotechnol., Biochem. 2005, 69, 391. (d) Brady, T. P.; Kim,
S. H.; Wen, K.; Kim, C.; Theodorakis, E. A. Chem. Eur. J.
2005, 11, 7175. (e) Ghosh, A. K.; Leshchenko, S.; Noetzel,
M. J. Org. Chem. 2004, 69, 7822. (f) García Ruano, J. L.;
Andres, J. I.; Fraile, A.; Martín Castro, A. M.; Martín, M. R.
Tetrahedron Lett. 2004, 45, 4653. (g) Trost, B. M.;
Crawley, M. L. Chem. Eur. J. 2004, 10, 2237. (h) Trost, B.
M.; Toste, F. D. J. Am. Chem. Soc. 2003, 125, 3090. (i) van
Oeveren, A.; Jansen, F. G. A.; Feringa, B. L. J. Org. Chem.
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(2) (a) Stecko, S.; Paśniczek, K.; Jurczak, M.; Urbańczyk-
Lipkowska, Z.; Chmielewski, M. Tetrahedron: Asymmetry
2007, 18, 1085. (b) García Ruano, J. L.; Fraile, A.; Martín,
M. R.; Núñez, A. J. Org. Chem. 2006, 71, 6536; and
references cited therein. (c) Trivedi, G. K. J. Indian Chem.
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(3) (a) Banwell, M. G.; Edwards, A. J.; MacLeod, M. D.;
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44, 931; and references cited therein. (c) Takadoi, M.;
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Synthesis 2009, No. 7, 1095–1098 © Thieme Stuttgart · New York