Tmsi-promoted diastereoselective synthesis of 5-(1'-Hydroxy)-γ- butyrolactones

Article abstract of DOI:10.1080/00397911.2010.502985

Trimethylsilyl iodide (TMSI) was found to be an efficient catalyst for the vinylogous Mukaiyama aldol reaction of 2-(trimethylsilyloxy)furan with various aldehydes with good diastereoselection. The reaction proceeds rapidly in CH ₂Cl₂ affording the corresponding 5-(hydroxy(aryl)methyl) furan-2(5H)-ones in good yields. This method offers significant advantages such as efficiency, generality, and mild reaction conditions with shorter reaction time. Copyright

Full text of DOI:10.1080/00397911.2010.502985

This article was downloaded by: [Fordham University]
On: 18 December 2012, At: 09:08
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic Organic
Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lsyc20
TMSI-Promoted Diastereoselective
Synthesis of 5-(1′-Hydroxy)-γ-
butyrolactones
Gowravaram Sabitha a , M. Nagendra Prasad a & J. S. Yadav a
a Organic Division I, Indian Institute of Chemical Technology,
Hyderabad, India
Version of record first published: 25 May 2011.
To cite this article: Gowravaram Sabitha, M. Nagendra Prasad & J. S. Yadav (2011): TMSI-Promoted
Diastereoselective Synthesis of 5-(1′-Hydroxy)-γ-butyrolactones, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 41:15, 2290-2295
To link to this article: http://dx.doi.org/10.1080/00397911.2010.502985
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representation
that the contents will be complete or accurate or up to date. The accuracy of any
instructions, formulae, and drug doses should be independently verified with primary
sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand, or costs or damages whatsoever or howsoever caused arising directly or
indirectly in connection with or arising out of the use of this material.

Synthetic Communications1, 41: 2290–2295, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.502985
TMSI-PROMOTED DIASTEREOSELECTIVE SYNTHESIS
OF 5-(1’-HYDROXY)-c-BUTYROLACTONES
Gowravaram Sabitha, M. Nagendra Prasad, and J. S. Yadav
Organic Division I, Indian Institute of Chemical Technology, Hyderabad,
India
GRAPHICAL ABSTRACT
Abstract Trimethylsilyl iodide (TMSI) was found to be an efficient catalyst for the
vinylogous Mukaiyama aldol reaction of 2-(trimethylsilyloxy)furan with various aldehydes
with good diastereoselection. The reaction proceeds rapidly in CH2Cl2 affording the
corresponding 5-(hydroxy(aryl)methyl)furan-2(5H)-ones in good yields. This method
offers significant advantages such as efficiency, generality, and mild reaction conditions
with shorter reaction time.
Keywords Aldehydes; butyrolactones; diastereoselection; TMSI; TMSOF
INTRODUCTION
The 5-(10-hydroxy)-c-butyrolactone subunit is present in a wide variety of
natural products with medicinal importance[1–9] and has also been employed as use-
ful intermediate in organic synthesis.[10–14] Even though several methods have been
developed for the synthesis of a-hydroxy-c-butyrolide, such as from chiral sulfox-
ides,[15] lactonization of epoxides,[16] and osmium-catalyzed asymmetric dihydroxy-
lation of c,d-unsaturated esters,[17–19] the most extensively used methodology is the
vinylogous aldol[20] addition with suitable furan derivatives. Recently, bismuth tri-
flate has been reported for this transformation.[21] The catalytic coupling of the com-
mercial 2-trimethylsilyloxyfuran (TMSOF) with aldehydes by means of aldol
reaction has emerged as an important strategy for buterolide synthesis.[10] In recent
years, many racemic examples of vinylogous Mukaiyama aldol with silyloxyfurans
have been reported using Lewis acids as catalysts, such as SnCl4, ZnCl2, TiCl4,
Received February 2, 2010.
Address correspondence to Gowravaram Sabitha, Organic Division I, Indian Institute of Chemical
Technology, Hyderabad 500 007, India. E-mail: gowravaramsr@yahoo.com
2290

5-(10-HYDROXYL)-c-BUTYROLACTONES
2291
Scheme 1. Synthesis of butyrolactones.
Table 1. Reactions of various aldehydes with 2-(trimethylsilyloxy)furan
Entry
Aldehyde RCHO 1
Product
Time (h)
dr (syn=anti)
Yield (%)
93
l
3a/4a
1.0
80:20
2
3
3b/4b
3c/4c
1.5
75:25
72:28
90
88
0.75
4
5
3d/4d
3e/4e
2.0
2.0
70:30
70:30
80
82
6
7
3f/4f
1.0
0.5
75:25
75:25
91
85
3g/4g
8
9
3h/4h
3i/4i
0.6
0.9
72:28
70:30
80
88
aAll products were characterized by 1H NMR, IR, and mass spectral data.

2292
G. SABITHA, M. N. PRASAD, AND J. S. YADAV
BF3 ꢀ OEt2, SiCl4, or silyltriflates.[22–24] Thus, the development of an efficient and ver-
satile method for the preparation of c-butyrolactones is an active ongoing research
area, and there is scope for further improvement in mild reaction conditions and
improved yields. The versatility of iodotrimethylsilane as a useful reagent in organic
synthesis is well established.[25–28] As a continuation of our studies on trimethylsilyl
iodide (TMSI),[29–31] we report in this communication a TMSI (generated in situ
from TMSCl and NaI in dichloromethane)–mediated diastereoselective Mukaiyama
aldol reaction of 2-(trimethylsilyloxy)furan with various aldehydes. Accordingly, the
reaction of TMSOF 2 with benzaldehyde 1 in the presence of in situ–generated
TMSI in CH2Cl2 at ꢁ78 ꢂC gave the 5-(hydroxy(phenyl)methyl)furan-2(5H)-one
(c-butenolide) as a mixture of syn and anti isomers 3a and 4a in 93% yield. The
complete conversion was observed in 1 h, providing the product with good diaster-
eoselectivity (Scheme 1). The syn and anti isomers (92:8) were separated by silica-gel
column chromatography and characterized by spectral data.
Encouraged by this result, a wide variety of aromatic aldehydes were reacted
with TMSOF under similar conditions, and the results are indicated in Table 1. In
all cases, the reaction proceeded rapidly at ꢁ78 ꢂC, affording the corresponding
butyrolactones 3b/4b–3i/4i in good yields. The electron-donating as well as
electron-withdrawing groups in aromatic aldehydes are well tolerated. We also
attempted to carry out the reaction with aliphatic aldehydes. Even though reactions
were successful, the yields were somewhat lower. The results of this study are also
shown in Table 1. The syn and anti isomers ratio was determined based on crude
1H NMR spectral data. a,b-Unsaturated and heteroaromatic aldehydes also under-
went this transformation smoothly to afford the corresponding c-butyrolactones in
1
good yields. All the products are confirmed by infrared (IR), H NMR, and mass
spectra data. In view of the potential applicability of this reaction in natural product
synthesis, this methodology using TMSI will be an attractive addition to the reported
procedures in terms of efficiency, short reaction times, good yields, and commercial
availability of TMSCl.
In summary, we have described a convenient and efficient protocol for the syn-
thesis of butyrolactones by the reaction of TMSOF with aldehydes. The significant
features of the present method are mild reaction conditions, simple experimental
procedure, good yields, and good diastereoselectivities. The scope and synthetic appli-
cation of this novel reaction can be applied for the synthesis of natural products.
EXPERIMENTAL
Typical Experimental Procedure of Compound 3a
NaI (0.149 mg, 1 mmol) and TMSCl (0.127 ml, 1 mmol) were added to a sol-
ution of the aldehyde 1 (106 mg, 1 mmol) in CH2Cl2, and the mixture was stirred
for 10 min. Then the reaction mixture was brought to ꢁ78 ꢂC, and a solution of
2-(trimethylsilyloxy)furan 2 (1 mmol) in CH2Cl2 was added dropwise. The reaction
mixture was stirred at ꢁ 78 ꢂC until the reaction was completed as indicated by
thin-layer chromatography (TLC). The reaction mixture was washed with Na2S2O3,
followed by brine, dried on Na2SO4, concentrated under reduced pressure, and
purified by silica-gel column chromatography to get the pure product 3a.

5-(10-HYDROXYL)-c-BUTYROLACTONES
2293
Spectral Data
Compound 3a (Threo isomer). White solid; mp 56–59 ꢂC: IR (KBr): cmꢁ1
1
3380, 1740, 1430, 1020, 810, 630; H NMR (CDCl3, 303 K, 300 MHz): d 7.41–7.27
(m, 5H), 7.17–7.11 (dd, J ¼ 6.0, 1.5, 1H), 6.08 (dd, J ¼ 6.043, 2.26, 1H), 5.10 (dt,
J ¼ 6.7, 1.5, 1H), 4.67 (d, J ¼ 6.7, 1H), 2.95 (brs, 1H). 13C NMR (CDCl3,
75 MHz): 173.1, 153.6, 138.1, 124.4, 128.3, 126.4, 122.3, 86.8, 75.1; LCMS (m=z):
191 (Mþ þ 1).
Compound 3a (Erythro isomer). White solid; mp 56–59 ꢂC: IR (KBr): cmꢁ1
3408, 1740, 1432, 820, 610; 1H NMR (CDCl3, 303 K, 300 MHz): d 7.43–7.26 (m, 6H),
6.17 (dd, J ¼ 6.04, 2.26, 1H), 5.14–5.09 (m, 2H), 2.8 (brs, 1H). 13C NMR (CDCl3,
75 MHz): 173.4, 153.2, 138.42, 128.0, 127.9, 126.0, 122.6, 86.5, 73.0. LCMS (m=z):
191 (Mþ þ 1).
Compound 3d (Mixture of diastereoisomers). White solid; mp 86–88 ꢂC:
1
IR (KBr): cmꢁ1 3390, 2935, 1712, 1450, 1026, 837, 706, 650. H NMR (CDCl3,
303 K, 300 MHz): d 7.57 [dd, J ¼ 5.3, 1.5, 1H (anti)], 7.44 [dd, J ¼ 5.3, 1.5, 1H
(syn)], 6.18 [dd, J ¼ 5.8, 2.2 (anti)], 6.15 [dd, J ¼ 5.8, 2.2 (syn)], 4.96 [m, 1H (anti)],
4.91 [m, 1H (syn)], 3.82 [m, 1H (anti)], 3.72 [m, 1H (anti)], 1.50–1.84 (m, 22H),
0.88 (m, 3H). LCMS (m=z): 307 (Mþ þ Na).
ACKNOWLEDGMENT
MNP thanks the Council of Scientific and Industrial Research (CSIR), New
Delhi, for the award of fellowship.
REFERENCES
1. Matsuura, D.; Takabe, K.; Yoda, H. Novel and stereocontrolled asymmetric synthesis of
a new naturally occurring styryllactone, (þ)-cardiobutanolide. Tetrahedron Lett. 2006, 47,
1371–1374.
2. Murakami, T.; Morikawa, Y.; Hashimoto, M.; Okuno, T.; Harada, Y. Lambertellols A
and B, novel 3,4-dihydronaphthalen-1(2H)-ones with spiro-butenolide produced by
Lambertella sp. 1346. Org. Lett. 2004, 6, 157–160.
3. Kumar, P.; Naidu, S. V.; Gupta, P. Efficient total synthesis of sapinofuranone B. J. Org.
Chem. 2005, 70, 2843–2846.
4. Li, Y.; Zhang, D.; Li, J.; Yu, S.; Li, Y.; Luo, Y. Hepatoprotective sesquiterpene glycosides
from Sarcandra glabra. J. Nat. Prod. 2006, 69, 616–620.
5. Li, J. Y.; Strobel, G.; Harper, J.; Lobkovsky, E.; Clardy, J. Cryptocin, a potent tetramic
acid antimycotic from the endophytic fungus Cryptosporiopsis cf. quercina. Org. Lett.
2000, 2, 767–770.
`
6. Pichon, M.; Hocquemiller, R.; Figadere, B. Synthesis of C1–C32 fragment of aza-solamin,
an unnatural analogue of the annonaceous acetogenin solamin. Tetrahedron Lett. 1999,
40, 8567–8570.
7. Yakura, T.; Matsumura, Y.; Ikeda, M. Formal total synthesis of clausenamide. Synlett.
1991, 343–344.
8. Corey, E. J.; Li, W. Z.; Nagamitsu, T.; Fenteany, G. The structural requirements for inhi-
bition of proteasome function by the lactacystin-derived b-lactone and synthetic analogs.
Tetrahedron 1999, 55, 3305–3316.

2294
G. SABITHA, M. N. PRASAD, AND J. S. YADAV
9. Fukuda, N.; Sasaki, K.; Sastry, T. V. R. S.; Kanai, M.; Shibasaki, M. Catalytic asymmet-
ric total synthesis of (þ)-lactacystin. J. Org. Chem. 2006, 71, 1220–1225.
10. Rassu, G.; Zanardi, F.; Battistini, L.; Casiraghi, G. The vinylogous aldol addition of
heterocyclic silyloxy dienes: Application in synthesis. Synlett. 1999, 1333–1350.
11. Hanessian, S.; Giroux, S.; Buffat, M. Total synthesis and structural confirmation of
(þ)-longicin. Org. Lett. 2005, 7, 3989–3992.
12. Konno, H.; Hiura, N.; Makabe, H.; Abe, M.; Miyoshi, H. Synthesis and mitochondrial
complex I inhibition of dihydroxy-cohibin A, non-THF annonaceous acetogenin ana-
logue. Bioorg. Med. Chem. Lett. 2004, 14, 629–632.
13. Ghosh, A. K.; Gong, G. Total synthesis and structural revision of (þ)-amphidinolide.
J. Am. Chem. Soc. 2004, 126, 3704–3705.
14. Casiraghi, G.; Rassu, G.; Auzzas, L.; Burreddu, P.; Gaetani, E.; Battistini, L.; Zanardi,
F.; Curti, C.; Nicastro, G.; Belvisi, L.; Motto, I.; Castorina, M.; Giannini, G.; Pisano,
C. Grafting aminocyclopentane carboxylic acids onto the RGD tripeptide sequence
generates low nanomolar aVb3=aVb5 integrin dual binders. J. Med. Chem. 2005, 48,
7675–7687.
15. Bravo, P.; Resnatl, G.; Vlani, F.; Arnone, A. Synthesis of the (4S, 5 R)-5-hydroxy-decan-
4-olide (L-factor) and of the (R)-decan-4-olide from a chiral sulphoxide. Tetrahedron
1987, 43, 4635–4647.
16. Sa¨ıah, M.; Bessodes, M.; Antonakis, K. Regioselective opening of chiral hydroxy epox-
ides: A short route to muricatacin and its diastereomer epi-muricatacin. Tetrahedron Lett.
1993, 34, 1597–1598.
17. (a) Janecki, T.; Blaszczyk, E. Stereocontrolled synthesis of 5-(10-hydroxyalkyl)-
3-methylidenetetrahydro-2-furanones. Tetrahedron Lett. 2001, 42, 2919–2922.
18. Wang, Z.; Zhang, X.; Sharpless, K. B.; Sinha, S. C.; Sinha-Bagchi, A.; Keinan, E. A gen-
eral approach to c-lactones via osmium-catalysed asymmetric dihydroxylation synthesis
of (–)-and (þ)-muricatacin. Tetrahedron Lett. 1992, 33, 6407–6410.
19. Casiraghi, G.; Zanardi, F.; Appendino, G.; Rassu, G. The vinylogous aldol reaction: A
valuable, yet understated carbon–carbon bond-forming maneuver. Chem. Rev. 2000,
100, 1929–1972.
20. For a review, see Rassu, G.; Zanardi, F.; Battistini, L.; Casiraghi, G. The synthetic utility of
furan-, pyrrole, and thiophene-based 2-silyloxy dienes. Chem. Soc. Rev. 2000, 29, 109–118.
21. Sarma, K. D.; Zhang, J.; Curran, T. T. Novel synthons from mucochloric acid: The first
use of a,b-dichloro-c-butenolides and c-butyrolactams for direct vinylogous aldol
addition. J. Org. Chem. 2007, 72, 3311–3318.
22. Acocella, M. R.; De Rosa, M.; Massa, A.; Palombi, L.; Villano, R.; Scettri, A. Silicon
tetrachloride in organic synthesis: New applications for the vinylogous aldol reaction.
Tetrahedron 2005, 61, 4091–4097.
23. Kong, K.; Romo, D. Diastereoselective, vinylogous Mukaiyama aldol additions of sily-
loxy furans to cyclic ketones: Annulation of butenolides and c-lactones. Org. Lett.
2006, 8, 2909–2912.
24. For a recent organocatalytic approach, see De Rosa, M.; Citro, L.; Soriente, A. The first
organocatalytic addition of 2-trimethylsilyloxyfuran to carbonyl compounds:
Hydrogen-bond catalysis in c-butenolides synthesis. Tetrahedron Lett. 2006, 47, 8507–
8510.
25. Aversa, M. C.; Barattucci, A.; Bonaccorsi, P.; Giannetto, P.; Policicchio, M. Unexpected
conversion of vinyl sulfoxides into carbonyl compounds by means of iodotrimethylsilane.
Tetrahedron Lett. 2000, 41 (22), 4441–4445.
26. Daley, L.; Meresse, P.; Bertounesque, E.; Monneret, C. A one-pot, efficient synthesis of
the potent cytotoxic podophyllotoxin derivative NPF. Tetrahedron Lett. 1997, 38 (15),
2673–2676.

5-(10-HYDROXYL)-c-BUTYROLACTONES
2295
27. Fisher, J. W.; Dunigan, J. M.; Hatfield, L. D.; Hoying, R. C.; Ray, J. E.; Thomas, K. L.
Cleavage of chiral 4-phenyl-2-oxalidinones with TMSI: Application to the synthesis of
carbacephems. Tetrahedron Lett. 1993, 34 (30), 4755–4758.
28. Aversa, M. C.; Barattucci, A.; Bonaccorsi, P.; Giannetto, P. An investigation of
the behaviour of a,b-unsaturated sulfoxides in the presence of trimethylsilyl iodide.
Tetrahedron 2002, 58 (51), 10145–10150.
29. Sabitha, G.; Reddy, K. B.; Bhikshapathi, M.; Yadav, J. S. TMSI-mediated Prins-type
cyclization of ketones with homoallylic and homopropargylic alcohol: Synthesis of
2,2-disubstituted-, spirocyclic-4-iodo-tetrahydropyrans and 5,6-dihydro-2H-pyrans.
Tetrahedron Lett. 2006, 47 (16), 2807–2810.
30. Sabitha, G.; Reddy, G. S. K. K.; Reddy, C. S.; Yadav, J. S. A novel TMSI-mediated syn-
thesis of Hantzsch 1,4-dihydropyridines at ambient temperature. Tetrahedron Lett. 2003,
44 (21), 4129–4131.
31. Sabitha, G.; Yadav, J. S. Reductive cleavage of phthalides with iodotrimethylsilane.
Synth. Commun. 1998, 28, 3065–3071.