Tandem Catalysis by Lipase in a Vinyl Acetate-Mediated Cross-Aldol Reaction
References
[1] a) F. F. Huerta, A. B. E. Minidis, J.-E. Backvall, Chem.
Soc. Rev. 2001, 30, 321–331; b) O. Pamies, J.-E. Back-
vall, Chem. Rev. 2003, 103, 3247–3261; c) M. J. Kim, Y.
Ahn, J. Park, Curr. Opin. Biotechnol. 2002, 13, 578–
587; d) J. C. Wasilke, S. J. Obrey, R. T. Baker, G. C.
Bazan, Chem. Rev. 2005, 105, 1001–1020.
[2] a) B. A. C. van As, J. V. Buijtenen, A. Heise, Q. B.
Broxterman, G. K. M. Verzijl, A. R. A. Palmans, E. W.
Meijer, J. Am. Chem. Soc. 2005, 127, 9964–9965; b) A.
Palmans, B. V. As, J. V. Buijtenen, L. V. der Mee, E. W.
Meijer, Polym. Prepr. Am. Chem. Soc. Div. Polym.
Chem. 2006, 47, 251–252.
[3] a) R. Mahrwald, Modern Aldol Reactions, Vol. 1, 2nd
edn., Weinheim, Wiley-VCH, 2004; b) G. Guillena, C.
Najera, D. J. Ramon, Tetrahedron: Asymmetry 2007, 18,
2249–2293; c) T. D. Machajewski, C. H. Wong, Angew.
Chem. 2000, 112, 1406–1430; Angew. Chem. Int. Ed.
2000, 39, 1352–1374.
[4] T. V. Vasudevan, M. Sharma, Ind. Eng. Chem. Process
Des. Dev. 1983, 22, 161–165.
[5] D. Mukherjee, B. A. Shah, P. Gupta, S. C. Taneja, J.
Org. Chem. 2007, 72, 8965–8968.
[6] M. B. Boxer, H. Yamamoto, J. Am. Chem. Soc. 2006,
128, 48–49.
[7] S. E. Denmark, T. Bui, J. Org. Chem. 2005, 70, 10190–
10193.
[8] M. B. Boxer, H. Yamamoto, J. Am. Chem. Soc. 2007,
129, 2762–2763 and references cited therein.
[9] J. W. Yang, C. Chandler, M. Stadler, D. Kampen, B.
List, Nature 2008, 452–455.
Scheme 1. Plausible mechanism of enol acetates mediated
aldol reaction.
Experimental Section
[10] Y. Hayashi, T. Itoh, S. Aratake, H. Ishikawa, Angew.
Chem. 2008, 120, 2112–2114; Angew. Chem. Int. Ed.
2008, 47, 2082–2084.
Typical Procedure (Table 2, Entry 1, Product A)
Vinyl acetate (276 mL, 4.0 mmol) was added to a mixture of
TEA (28 mL, 20 mol%), 2-propanol (306 mL, 4.0 mmol), No-
vozym435 lipase (1 mg) and p-nitrobenzaldehyde in a 2.0-
mL microcentrifuge tube and kept on shaking at room tem-
perature. After 24 h, vinyl acetate (276 mL, 4.0 mmol) and 2-
propanol (306 mL, 4.0 mmol) were added to the reaction
mixture. The reaction mixture was shaked for a total of
60 h, then cooled to 08C and MeOH (2.0 mL) and NaBH4
(226.5 mg, 6 mmol) were added, and the mixture was stirred
for 1 h at 08C. The reaction was quenched with pH 7.0 phos-
phate buffer solution, the organic materials were extracted
with ethyl acetate three times, and then the combined or-
ganic extracts were dried over anhydrous sodium sulphate,
and concentrated under vacuum after filtration. Purification
through column chromatography gave 1-(4’-nitrophenyl)
propane-1,3-diol; yield: 72%.
[11] Y. Hayashi, S. Samanta, T. Itoh, H. Ishikawa, Org. Lett.
2008, 10, 5581–5583.
[12] a) Y. Hayashi, T. Itoh, M. Ohkubo, H. Ishikawa,
Angew. Chem. 2008, 120, 4800–4802; Angew. Chem.
Int. Ed. 2008, 47, 4722–4724; b) P. G. Garcia, A. Lade-
peche, R. Halder, B. List, Angew. Chem. 2008, 120,
4797–4799; Angew. Chem. Int. Ed. 2008, 47, 4719–
4721.
[13] Y. Hayashi, T. Okano, T. Itoh, T. Urushima, H. Ishika-
wa, T. Uchimaru, Angew. Chem. 2008, 120, 9193–9198;
Angew. Chem. Int. Ed. 2008, 47, 9053–9058.
[14] a) S. M. Dean, W. A. Greenberg, C. H. Wong, Adv.
Synth. Catal. 2007, 349, 1308–1320; b) J. Liu, C. C.
Hsu, C. H. Wong, Tetrahedron Lett. 2004, 45, 2439–
2441.
[15] E. M. Lopez, R. P. Herrera, M. Christmann, Nat. Prod.
Rep. 2010, 27, 1138–1167.
[16] N. Hara, S. Nakamura, N. Shibata, T. Toru, Adv. Synth.
Catal. 2010, 352, 1621–1624.
[17] N. Hara, S. Nakamura, N. Shibata, T. Toru, Chem. Eur.
Acknowledgements
J. 2009, 15, 6790–6793.
[18] T. Itoh, H. Ishikawa, Y. Hayashi, Org. Lett. 2009, 11,
3854–3857.
[19] a) T. Mukaiyama, T. Izawa, K. Saigo, K. Chem. Lett.
1974, 323–326; b) Y. Masuyama, T. Sakai, Y. Kurusu,
Tetrahedron Lett. 1993, 34, 653–656; c) Y. Masuyama,
Y. Kobayashi, R. Yanagi, Y. Kurusu, Chem. Lett. 1992,
We thank Department of Science and Technology, India for
support of our work. One of the authors M.K. thanks CSIR,
New Delhi for the award of a junior research fellowship.
Adv. Synth. Catal. 2011, 353, 1207 – 1212
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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