The sulfinyl moiety as an intramolecular nucleophile. Part 3: Synthesis of (-)-muricatacin

Article abstract of DOI:10.1016/S0957-4166(02)00782-6

A short, efficient and highly stereoselective synthesis of (-)-(R,R)-muricatacin is reported. The key steps include a highly diastereoselective reduction of a β-ketosulfoxide to a β-hydroxy sulfoxide, regio- and stereoselective bromohydration of an olefin

Full text of DOI:10.1016/S0957-4166(02)00782-6

TETRAHEDRON:
ASYMMETRY
Pergamon
Tetrahedron: Asymmetry 14 (2003) 101–105
The sulfinyl moiety as an intramolecular nucleophile. Part 3:
Synthesis of (−)-muricatacin†
Sadagopan Raghavan* and S. C. Joseph
Organic Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 9 November 2002; accepted 16 November 2002
Abstract—A short, efficient and highly stereoselective synthesis of (−)-(R,R)-muricatacin is reported. The key steps include a
highly diastereoselective reduction of a b-ketosulfoxide to a b-hydroxy sulfoxide, regio- and stereoselective bromohydration of an
olefin employing the sulfinyl group as an internal nucleophile and chemoselective reduction of a double bond in the presence of
a halogen atom. © 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
via early transition states resembling p-complexes, while
the reactions of substrates with external nucleophiles
proceed via late transition states resembling onium
ions. This difference affects the facial selectivity of
electrophilic attack. We have been interested in the
electrophile induced heterofunctionalisation of allylic
olefins using the sulfinyl group as an internal
nucleophile7 and herein, we report a short, efficient and
a highly stereoselective synthesis of (−)-muricatacin
exploiting this methodology.
The addition of nucleophiles to double bonds activated
by complexation with electrophiles affords highly func-
tionalized products. A substituent at the allylic or
homoallylic position directs the regio- and stereochem-
istry of the reaction1 and the steric2 and/or stereoelec-
tronic effects3 from the substituent have been invoked
to rationalize the outcome of such reactions. The asym-
metric induction is also a function of the double bond
geometry,4 reaction conditions (thermodynamic versus
kinetic control)5 and whether the nucleophile attacks
intramolecularly or intermolecularly6 especially for elec-
trophiles such as I2, NBS (N-bromosuccinimide),
Hg(OAc)2 and PhSeCl. Substrates with an internal
nucleophile have been shown to react with electrophiles
Muricatacin 1, isolated from the seeds of Annona muri-
cata L.8 is probably a product of oxidative cleavage of
its monotetrahydrofuranic acetogenin congeners9 2–7
(Fig. 1). The isolated sample is a mixture of enan-
tiomers, with the (−)-(R,R) enantiomer predominating.
Figure 1.
* Corresponding author. E-mail: purush101@yahoo.com
† IICT Communication No. 021107.
0957-4166/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(02)00782-6

102
S. Ragha6an, S. C. Joseph / Tetrahedron: Asymmetry 14 (2003) 101–105
Muricatacin is a member of the hydroxy lactone class
of compounds, that are notable for their biological
activity10 and as building blocks in the synthesis of both
complex bioactive natural products11 and synthetic
compounds.12 Muricatacin is biologically active show-
ing cytotoxicity in KB and VERO cell lines. It has
stimulated a great deal of attention due its biological
activity and many syntheses13 have been reported in the
literature.
the sulfonium salt followed by hydrolysis through
attack of water on sulfur18 (Fig. 2).
Treatment of the bromodiol 10 with 2,2-
dimethoxypropane in the presence of catalytic CSA
afforded the acetonide 16, the 13C spectrum of which
revealed signals for the methyl groups at l 27.1, 27.4
and for the quaternary carbon at l 110.3 proving
unambiguously19 the syn-disposition of the hydroxy
groups in 10. Subjecting the acetonide 16 to Pummerer
reaction20 followed by aqueous NaHCO3 workup of the
intermediate, afforded the aldehyde which, without
purification, was used directly in the next step. Thus,
treatment of the aldehyde with methyl(triphenylphos-
phoranylidene)acetate in benzene afforded a mixture of
the cis- and trans-olefins (17 and 18, respectively) in
equimolar quantities. The cis- and trans-olefins were
not separated (except for analytical purposes) and were
subjected to hydrogenation over Pt/C in EtOAc as the
solvent to yield the acetonide 19. Deprotection of the
acetonide by treatment with catalytic CSA in methanol
led to concomitant cyclisation of the resulting hydroxy
ester to afford the bromolactone 20. Treatment of 20
with Ag2O in acetonitrile afforded the epoxide 8 which
was identical in all respects to the sample prepared by
Depezay and co-workers.13 Finally, reaction of the
epoxy lactone 8 with an excess of undecylmagnesium
bromide in the presence of Li2CuCl4 afforded (−)-muri-
catacin 1 (Scheme 3). It is instructive to note that
starting from the diastereomer of 11 (that differs at the
hydroxyl center) and using the above methodology,
(+)-muricatacin can be elaborated.
2. Results and discussion
Retrosynthetic analysis (Scheme 1) shows that muricat-
acin 1 can be derived from the epoxy lactone 8, which
can be readily obtained from the bromoester 9. The
synthesis of 9 can be envisaged from the sulfoxide 10,
which in turn can be secured from the olefin 11.
The synthesis began with the allyl alcohol 11, which
was obtained by diastereoselective reduction14 (>95%
de) of the b-ketosulfoxide 14 with DIBALH. Com-
pound 14 was obtained by condensation of the anion of
(R)-tolyl methyl sulfoxide 12,15 with 1-imidazolyl-2-
propen-1-one 13.16 It is informative to note that the
condensation of ethyl acrylate with the anion of tolyl
methyl sulfoxide afforded predominantly the conjugate
addition product 15 and none of the ketosulfoxide 14.
Treatment of the olefin 11 with NBS in the presence of
water in toluene as the solvent afforded bromohydrin
107a stereospecifically (Scheme 2).
The formation of the bromohydrin 10 can be rational-
ized by the attack of bromonium ion on the olefin 11 in
the depicted conformation17 from the side of the hydro-
gen atom followed by intramolecular nucleophilic
attack by the sulfinyl group in a 5-exo mode to afford
Figure 2.
Scheme 1.
Scheme 3. Reaction conditions: (a) 2,2-DMP, cat. CSA, acet-
one, rt, 92%. (b) (i) TFAA, Et3N, CH2Cl2, 0°C, 15 min then
aq. NaHCO3; (ii) Ph3PCHCO2Me, PhH, rt, 1:1 of 17:18, 58%
for two steps. (c) H2, Pt/C, EtOAc, rt, 94%. (d) Cat. CSA,
MeOH, rt, 84%. (e) Ag2O, CH3CN, rt, 81%. (f) C12H25MgBr,
Li2CuCl4, −78°C to rt 36 h, 72%.
Scheme 2. Reaction conditions: (a) (R)-TolS(O)Me, LDA,
THF, −30°C, −15°C, add 13, 78%. (b) DIBAH, THF, −78°C,
93%. (c) NBS, H2O, toluene, rt, 81%.

S. Ragha6an, S. C. Joseph / Tetrahedron: Asymmetry 14 (2003) 101–105
103
In summary, we have devised a stereo- and regiospecific
route to muricatacin from b-hydroxy sulfoxide 11. The
key steps include diastereoselective reduction of a b-
keto sulfoxide, bromohydrin formation by neighbour-
ing group participation from the sulfinyl moiety. This
affords efficient 1,2-asymmetric induction and chemose-
lective reduction of the double bond of 17 and 18 in the
presence of a labile halogen atom. The strategy adopted
is flexible and should allow the synthesis of other
members of the hydroxy lactone class of compounds.
residue was treated with 10% aq. NaOH solution. The
aq. layer was extracted with ether and the organic layer
washed successively with water, brine and dried over
Na2SO4. The solvent was removed in vacuo and the
crude product was purified by column chromatography
using 30% EtOAc/pet. ether as eluent to afford 11 (2.92
1
g, 93%). Solid. Mp 81°C. H NMR (200 MHz, CDCl3)
l 7.52 (d, J=8.0 Hz, 2H), 7.32 (d, J=8.0 Hz, 2H), 5.80
(ddd, J=17.0, 10.3, 5.7 Hz, 1H), 5.34 (d, J=17.0 Hz,
1H), 5.12 (d, J=10.3 Hz, 1H), 4.70 (s, 1H), 4.40 (br s,
1H), 2.95 (dd, J=10.4, 6.0 Hz, 1H), 2.72 (dd, J=10.4,
1.5 Hz, 1H), 2.42 (s, 3H). 13C NMR (50 MHz, CDCl3)
l 141.2, 140.3, 138.6, 129.9, 123.9, 115.5, 66.7, 63.3,
21.3. MS (EI) 210 (M+). [h]D +134.0 (c 1, acetone).
3. Experimental
Melting points were recorded on Buchi R-535 appara-
tus and are uncorrected. 1H NMR spectra were
recorded on Gemini-200 and Brucker 300 spectropho-
tometers in CDCl3 using TMS as internal standard.
Mass spectra were recorded on a Finnigan Matt 1200
mass spectrometer operating at 70 eV. Optical rotations
were measured on a Jasco Dip 360 Digital polarimeter.
Column chromatography was performed on silica gel
(Merck, 100–200 mesh).
3.3. 1-Bromo-(4S)-(4-methylphenylsulfinyl)-(2S,3S)-
butane-2,3-diol, 10
To a solution of the unsaturated sulfoxide (11) (2.1 g,
10 mmol) in toluene (40 mL) was added water (0.27
mL, 15 mmol) followed by freshly recrystallized NBS
(0.94 g, 12 mmol) and the mixture stirred at rt for 30
min. The reaction mixture was then diluted with ether
and the organic layer washed successively with 5% aq.
NaHCO3, water, brine and dried over Na2SO4. The
solvent was removed under reduced pressure to afford
the crude product which was purified by column chro-
matography using 40% EtOAc/pet. ether as eluent to
3.1. (1R)-(4-Methylphenylsulfinyl)-3-buten-2-one, 14
To a solution of acryloyl chloride (1.81 g, 20 mmol) in
dry THF (40 mL) was added imidazole (2.72 g, 40
mmol) at 0°C and the mixture was stirred for 10 min.
The salt was filtered and the filtrate (13) used directly in
the next step: to a solution of diisopropyl amine (4.72
mL, 33.8 mmol) in dry THF (47 mL) at 0°C was added
n-BuLi (1.6 M in hexanes, 21.1 mL, 33.8 mmol) drop-
wise and stirred for 10 min. LDA so generated was
cooled to −30°C and a solution of (R)-tolyl methyl
sulfoxide (3.47 g, 23 mmol) in dry THF (25 mL) was
added dropwise and stirred for 20 min. The reaction
mixture was then warmed to −15°C and the solution of
13 prepared above was added to it dropwise and stirred
for 20 min. The reaction was quenched by adding
saturated aq. ammonium chloride (10 mL). The reac-
tion mixture was extracted with ether. The combined
organic layers were washed with water, brine and dried
over Na2SO4. The solvent was removed under reduced
pressure to yield the crude product mixture which was
purified by column chromatography using 70% EtOAc/
pet. ether as eluent to afford 14 (3.26 g, 78%). Viscous
1
yield 10 (2.46 g) in 81% yield. Solid. Mp 108°C. H
NMR (200 MHz, CDCl3) l 7.54 (d, J=8.0 Hz, 2H),
7.35 (d, J=8.0 Hz, 2H), 4.70 (m, 1H), 3.54 (dd, J=
10.3, 7.3 Hz, 1H), 3.40 (dd, J=10.3, 6.4 Hz, 1H), 3.02
(dd, J=13.7, 8.0 Hz, 1H), 2.89 (dd, J=13.7, 3.4 Hz,
1H), 2.45 (s, 3H). 13C NMR (50 MHz, CDCl3) l 140.7,
140.0, 129.0, 123.0, 72.9, 64.8, 61.7, 33.3, 20.5. MS
(FAB) 306 (M++H). [h]D −208.2 (c 0.5, MeOH).
3.4. 4-Bromomethyl-2,2-dimethyl-5-(4-methyl-(S)-phenyl-
sulfinylmethyl)-(4S,5S)-1,3-dioxolane, 16
To the solution of the bromodiol (10) (1.83 g, 6.0
mmol) in acetone (15 mL) was added 2,2-
dimethoxypropane (5 mL) and catalytic amounts of
CSA and the mixture stirred at rt for 1 h. Et3N, enough
to neutralise CSA, was added and the volatiles were
removed under reduced pressure. The residue was
purified by column chromatography using 20% EtOAc/
pet. ether as the eluent to afford 16 (1.92 g) in 92%
1
1
liquid. H NMR (300 MHz, CDCl3) l 7.48 (d, J=8.0
yield. Solid. Mp 92°C. H NMR (200 MHz, CDCl3) l
Hz, 2H), 7.25 (d, J=8.0 Hz, 2H), 6.30 (dd, J=17.6,
10.4 Hz, 1H), 6.15 (d, J=17.6 Hz, 1H), 5.90 (d, J=10.4
Hz, 1H), 4.05 (d, J=13.6 Hz, 1H), 3.85 (d, J=13.6 Hz,
1H), 2.36 (s, 3H). 13C NMR (75 MHz, CDCl3) l 191.4,
142.3, 136.2, 131.6, 130.1, 124.2, 124.0, 65.8, 21.4. MS
(EI) 208 (M+). [h]D +184.6 (c 1, CHCl3).
7.55 (d, J=8.0 Hz, 2H), 7.32 (d, J=8.0 Hz, 2H), 4.25
(ddd, J=6.9, 6.4, 5.5 Hz, 1H), 3.94 (q, J=6.4, 1H),
3.52 (dd, J=11.0, 5.5 Hz, 1H), 3.41 (dd, J=11, 6.9 Hz,
1H), 3.12 (d, J=6.4 Hz, 2H), 2.42 (s, 3H), 1.44 (s, 3H),
1.39 (s, 3H). 13C NMR (50 MHz, CDCl3) l 141.5,
130.0, 124.4, 110.3, 78.7, 75.3, 60.2, 31.3, 27.4, 27.1,
21.6. MS (EI) 346 (M+). [h]D −202.3 (c 1, CHCl3).
3.2. (1R)-(4-Methylphenylsulfinyl)-(2S)-3-buten-2-ol, 11
3.5. Methyl 3-[5-bromomethyl-2,2-dimethyl-(4R,5S)-1,3-
dioxolan-4-yl]-(Z)-2-propenoate, 17 and methyl 3-[5-bro-
momethyl-2,2-dimethyl-(4R,5S)-1,3-dioxolan-4-yl]-(E)-2-
propenoate, 18
To a solution of ketosulfoxide (14) (3.12 g, 15 mmol) in
dry THF (65 mL) cooled at −78°C was added a solu-
tion of DIBAL (2 M in toluene, 7.5 mL) and stirred for
2 h. The reaction was quenched by the addition of
methanol (60 mL) and allowed to attain rt. The sol-
vents were removed under reduced pressure and the
To the solution of the bromoacetonide (16) (1.74 g, 5
mmol) in dichloromethane (20 mL) cooled at 0°C was

104
S. Ragha6an, S. C. Joseph / Tetrahedron: Asymmetry 14 (2003) 101–105
added triethylamine (1.39 mL, 10 mmol) followed by
trifluoroacetic anhydride (1.41 mL, 10 mmol) and
stirred for 15 min. An aq. 5% NaHCO3 solution (25
mL) was added at 0°C and stirred for another 20 min.
The reaction mixture was then extracted into benzene
(40 mL) and washed successively with water, brine and
dried over Na2SO4. This benzene solution of the alde-
hyde was directly taken ahead to the next step and
reacted with methyl(triphenylphosporanilidine)acetate
(2.49 g, 6 mmol). The reaction was stirred at rt for 30
min. The solvent was removed under reduced pressure
to afford a residue which was purified by column
chromatography using 10% EtOAc/pet. ether as the
eluent to afford an equimolar mixture of cis-(17) and
trans-olefins (18) (0.81 g, 2.9 mmol) in 58% overall
yield for two steps. A small amount of this mixture
was separated to afford pure cis- and trans-isomers.
The bulk sample was however used as a mixture of
isomers in the next step. 17: Viscous oil. 1H NMR
(300 MHz, CDCl3) l 6.32 (dd, J=12.1, 7.7 Hz, 1H),
5.92 (d, J=12.1 Hz, 1H), 5.35 (t, J=7.7 Hz, 1H), 3.98
(td, J=7.7, 4.4 Hz, 1H), 3.76 (s, 3H), 3.62 (dd, J=
12.1, 4.4 Hz, 1H), 3.50 (dd, J=12.1, 7.0 Hz, 1H), 1.41
(s, 3H), 1.40 (s, 3H). 13C NMR (50 MHz, CDCl3) l
165.6, 146.3, 122.5, 110.5, 80.9, 75.9, 51.6, 32.3, 27.3.
MS (EI) 278 (M+). [h]D 118.5 (c 0.14, CHCl3). 18:
J=7.3 Hz, 2H), 2.62–2.40 (m, 2H), 2.40–2.20 (m, 2H).
13C NMR (75 MHz, CDCl3) l 177.0, 79.5, 73.1, 33.5,
28.2, 24.0. MS (EI) 208 (M+). [h]D −35.6 (c 0.19,
CHCl3).
3.8. 5-[(2R)-Oxiran-2-yl]-(5R)-2H,3H,4H-2-furanone, 8
To a solution of bromohydrin 20 (0.418 g, 2 mmol) in
CH3CN (20 mL) was added Ag2O (0.464 g, 2 mmol)
at 0°C and the mixture was stirred under an atmo-
sphere of nitrogen gradually allowing it to attain rt
over 2 h. The reaction mixture was filtered and the
filtrate evaporated in vacuo to afford the crude
product. Column chromatography using 40% EtOAc/
pet. ether as the eluent afforded 8 (0.208 g, 1.62
mmol) in 81% yield. Viscous liquid. 1H NMR (200
MHz, CDCl3) l 4.60 (m, 1H), 3.10 (m, 1H), 2.82–2.76
(m, 2H), 2.63 (m, 1H), 2.49 (m, 1H), 2.40 (m, 1H),
2.30 (m, 1H). 13C NMR (75 MHz, CDCl3) l 175.7,
76.4, 53.0, 43.6, 27.5, 25.0. MS (EI) 128 (M+). [h]D
−28.6 (c 1.64, CHCl3).
3.9. 5-[1-Hydroxy-(1R)-tridecyl]-(5R)-2H,3H,4H-2-
furanone, 1
1
Viscous oil. H NMR (300 MHz, CDCl3) l 6.92 (dd,
To a stirred solution of Li2CuCl4 (0.1 M/THF, 7.5
mL, 0.75 mmol) cooled at −35°C was added undecyl
magnesium bromide (1 M/THF, 7.5 mL, 7.5 mmol)
and stirred for 30 min at the same temperature. This
mixture was added to the solution of epoxy lactone 8
(0.192 g, 1.5 mmol) in anhydrous THF (7.5 mL)
cooled at −78°C. The reaction mixture was gradually
allowed to attain rt and stirred for 24 h. The reaction
mixture was cooled to −78°C and another portion of
the mixture of Li2CuCl4 and undecyl magnesium bro-
mide was added and stirred for another 12 h allowing
it to attain rt. The reaction was cooled to 0°C and
quenched by the addition of aq. satd. NH4OAc. The
layers were separated and the aq. layer extracted with
ether. The combined organic layers were washed suc-
cessively with water, brine and dried over Na2SO4.
The solvent was removed in vacuo and the residue
purified by chromatography using 30% EtOAc/pet.
ether as the eluent to afford 1 (0.305 g, 1.07 mmol) in
72% yield. Solid. Mp 72°C, lit. 71°C.13o 1H NMR (300
MHz, CDCl3) l 4.39 (m, 1H), 3.50 (m, 1H), 2.62–2.40
(m, 2H), 2.16 (m, 1H), 2.08 (m, 1H), 1.88 (m, 1H),
1.55 (m, 2H), 1.62–1.20 (m, 20H), 0.80 (t, J=6.0 Hz,
3H). 13C NMR (75 MHz, CDCl3) l 177.4, 83.0, 73.5,
32.9, 31.8, 29.6, 29.5, 29.4, 29.3, 28.6, 25.4, 24.0, 22.6,
14.0. MS (FAB) 285 (M++H). [h]D −22.8 (c 1.0,
CHCl3), lit. −22.9 (c 1.1, CHCl3).13a
J=16.0 Hz, 6.1 Hz, 1H), 6.12 (d, J=16.0 Hz, 1H),
4.45 (t, J=6.1 Hz, 1H), 3.95 (m, 1H), 3.73 (s, 3H),
3.45 (d, J=6.1, 1H), 1.41 (s, 3H), 1.40 (s, 3H). 13C
NMR (75 MHz, CDCl3) l 166.3, 143.9, 122.7, 110.8,
79.4, 79.2, 51.8, 31.1, 27.0. [h]D −9.2 (c 0.42, CHCl3).
3.6. Methyl 3-[5-bromomethyl-2,2-dimethyl-(4R,5S)-1,3-
dioxolan-4-yl]propanoate, 19
To a solution of the mixture of esters (0.70 g, 2.5
mmol) in EtOAc (10 mL) was added 5% Pt/C (70 mg)
and the mixture was stirred at rt for 4 h under an
atmosphere of hydrogen. The catalyst was removed by
filtration and the filtrate evaporated in vacuo to dry-
ness. The residue was purified by column chromatog-
raphy using 20% EtOAc/pet. ether as the eluent to
afford 19 (0.66 g, 2.35 mmol) in 94% yield. Viscous
1
oil. H NMR (300 MHz, CDCl3) l 3.90–3.81 (m, 2H),
3.67 (s, 3H), 3.48–3.36 (m, 2H), 2.58–2.40 (m, 2H),
2.05 (m, 1H), 1.81 (m, 1H), 1.38 (s, 6H). 13C NMR
(75 MHz, CDCl3) l 172.8, 109.3, 79.6, 79.3, 51.4, 31.7,
30.2, 28.7, 27.5, 27.2. MS (EI) 280 (M+). [h]D −15.7 (c
1.38, CHCl3).
3.7. 5-[2-Bromo-1-hydroxy-(1S)-ethyl]-(5R)-2H,3H,4H-
2-furanone, 20
To a solution of the bromoester 19 (0.63 g, 2.25
mmol) in methanol (2.3 mL) was added catalytic
amounts of CSA and the mixture was stirred at rt for
2 h. Et3N was added to neutralize the acid and
methanol was removed under reduced pressure. The
residue was purified by column chromatography using
40% EtOAc/pet. ether as the eluent to yield 20 (0.39 g,
Acknowledgements
S.R. is thankful to Dr. J. S. Yadav, Head, Org. Div. I
for constant support and encouragement. S.C.J. is
thankful to CSIR, New Delhi for a fellowship. Finan-
cial assistance from DST (New Delhi) is gratefully
acknowledged. We thank Dr. A. C. Kunwar for the
NMR spectra.
1
1.89 mmol) in 84% yield. Viscous oil. H NMR (200
MHz, CDCl3) l 4.68 (m, 1H), 3.78 (m, 1H), 3.45 (d,

S. Ragha6an, S. C. Joseph / Tetrahedron: Asymmetry 14 (2003) 101–105
105
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