Stereoselective Biooxidation of Cyclobutanones
FULL PAPERS
(S)-2g (yield: 69 mg, 0.32 mmol, 89%, 97% ee). Oxidation
of 1g (100 mg, 0.53 mmol) with CHMOBrevi1 gave (S)-2g
(yield: 80 mg, 0.39 mmol, 73%, 26% ee). Transformation of
1g (69 mg, 0.36 mmol) with CHMOBrevi2 gave (R)-2g (yield:
48 mg, 0.20 mmol, 64%, 24% ee). The crude product was
purified by column chromatography (LP/EtOAc=10/1) and
was obtained as a yellow odorous oil.[32]
Dihydro-4-(1,3-benzodioxo-5-ylmethyl)-furan-2(3H)-one
(2h): Biotransformation of 3-(1,3-benzodioxo-5-ylmethyl)-
cyclobutanone 1h (94 mg, 0.46 mmol) with CHMORhodo2
gave (S)-2h (yield: 53 mg, 0.24 mmol, 52%, 98% ee). Oxida-
tion of 1h (94 mg, 0.46 mmol) with CHMOBrevi1 gave (R)-2h
(yield: 62 mg, 0.28 mmol, 61%, 75% ee). Conversion of 1h
(94 mg, 0.46 mmol) with CHMOBrevi2 gave (S)-2h (yield:
53 mg, 0.24 mmol, 53%, 37% ee). The crude product was
purified via column chromatography (LP/EtOAc=6/1) and
was obtained as brown odorant oil.[33]
Dihydro-4-(3,4,5-trimethoxybenzyl)-furan-2(3H)-one (2i):
Biotransformation of 3-(3,4,5-trimethoxybenzyl)cyclobuta-
none (1i; 65 mg, 0.26 mmol) with CHMOArthro gave (S)-2i
(yield: 50 mg, 0.19 mmol, 72%, 94% ee). Oxidation of 1i
(65 mg, 0.26 mmol) with CHMOBrevi1 gave (R)-2i (yield:
50 mg, 0.26 mmol, 72%, 79% ee). The crude product was
purified via column chromatography (LP/EtOAc=2/1) and
isolated as colorless crystals;[34] mp 93–968C (Lit.[35] 98–
998C).
4-Benzyloxymethyldihydrofuran-2(3H)-one (2j): Biotrans-
formation of 3-benzyloxymethylcyclobutanone (1j; 116 mg,
0.61 mmol) with CHMOArthro gave (R)-2j (yield: 23 mg,
0.11 mmol, 18%, 58% ee). Oxidation of 1j (116 mg,
0.61 mmol) with CHMOBrevi1 gave (S)-2j (yield: 33 mg,
0.16 mmol, 26%, 55% ee). Transformation of 1j (116 mg,
0.61 mmol) with CHMOBrevi2 gave (R)-2j (67 mg, 0.32 mmol,
53%, 63% ee). The crude product was purified via column
chromatography (LP/EtOAc=2/1) and was obtained as a
yellow oil.[36]
[2] For reviews on stereoselective Baeyer–Villiger oxida-
tions see: a) M. D. Mihovilovic, F. Rudroff, B. Grçtzl,
Curr. Org. Chem. 2004, 8, 1057–1069; b) C. Bolm, Per-
oxide Chemistry, ed, Wiley-VCH: Weinheim, 2000,
pp 494–510 and references cited therein; c) G. Strukul,
Angew. Chem. Int. Ed. 1998, 37, 1198–1209.
[3] For recent reviews see: a) M. D. Mihovilovic, Curr.
Org. Chem. 2006, 10, 1265–1287; b) W. J. H. van Ber-
kel, N. M. Kamerbeek, M. W. Fraaije, J. Biotechnol.
2006, 670–689; c) N. M. Kamerbeek, D. B. Janssen,
W. J. H. van Berkel, M. W. Fraaije, Adv. Synth. Catal.
2003, 345, 667–678; d) M. D. Mihovilovic, B. Müller, P.
Stanetty, Eur. J. Org. Chem. 2002, 3711–3730; e) J. D.
Stewart, Curr. Org. Chem. 1998, 2, 195–216; f) S. M.
Roberts, P. W. H. Wan, J. Mol. Catal. B: Enzym. 1998,
4, 111–136; g) A. Willetts, Trends Biotechnol. 1997, 15,
55–62; h) C. T. Walsh, Y.-C. J. Chen, Angew. Chem.
1988, 100, 342–352.
[4] a) D. Bonsor, S. F. Butz, J. Solomons, S. Grant, I. J. S.
Fairlamb, M. J. Fogg, G. Grogan, Org. Biomol. Chem.
2006, 4, 1252–1260; b) M. W. Fraaije, N. M. Kamer-
beek, A. J. Heidekamp, R. Fortin, D. B. Janssen, J. Biol.
Chem. 2004, 279, 3354–3360; c) J. B. van Beilen, F.
Mourlane, M. A. Seeger, J. Kovac, Z. Li, T. H. M.
Smits, U. Fritsche, B. Witholt, Environ. Microbiol.
2003, 5, 174–182; d) P. Brzostowicz, D. M. Walters,
S. M. Thomas, V. Nagarajan, P. E. Rouviere, Appl. En-
viron. Microbiol. 2003, 69, 334–342; e) M. W. Fraaije,
N. M. Kamerbeek, W. J. H. van Berkel, D. B. Janssen,
FEBS Lett. 2002, 518, 43–47; f) P. C. Brzostowicz, K. L.
Gibson, S. M. Thomas, M. S. Blasko, P. E. Rouviere, J.
Bacteriol. 2000, 182, 4241–4248; g) J. D. Stewart, K. W.
Reed, C. A. Martinez, J. Zhu, G. Chen, M. M. Kayser,
J. Am. Chem. Soc. 1998, 120, 3541–3548; h) M. M.
Kayser, J. D. Stewart, J. Org. Chem. 1998, 63, 7103–
7106; i) J. D. Stewart, W. R. Kieth, J. Zhu, G. Chen,
M. M. Kayser, J. Org. Chem. 1996, 61, 7652–7653;
j) J. D. Stewart, K. W. Reed, M. M. Kayser, J. Chem.
Soc., Perkin Trans. 1 1996, 755–757.
[5] a) C. M. Clouthier, M. M. Kayser, M. T. Reetz, J. Org.
Chem. 2006, 71, 8431–8437; b) M. D. Mihovilovic, F.
Rudroff, A. Winninger, T. Schneider, F. Schulz, M. T.
Reetz, Org. Lett. 2006, 8, 1221–1224; c) M. Bocola, F.
Schulz, F. Leca, A. Vogel, M. W. Fraaije, M. T. Reetz,
Adv. Synth. Catal. 2005, 347, 979–986; d) M. T. Reetz,
B. Brunner, T. Schneider, F. Schulz, C. M. Clouthier,
M. M. Kayser, Angew. Chem. Int. Ed. 2004, 43, 4075–
4078.
[6] a) S. D. Doig, L. M. OꢁSullivan, S. Patel, J. M. Ward,
J. M. Woodley, Enzyme Microb. Technol. 2001, 28,
265–274; b) G. Chen, M. M. Kayser, M. D. Mihovilov-
ic, M. E. Mrstik, C. A. Martinez, J. D. Stewart, New J.
Chem. 1999, 8, 827–832.
Acknowledgements
This project was funded by the Austrian Science Fund (FWF,
Project No. P16373) and by the European Union under the
5th Framework Programme within the Marie-Curie Training
Site GEMCAT (contract no.: HPMT-CT-2001–00243). Sup-
port by Vienna University of Technology is acknowledged to-
gether with a mobility grant for F.H.O. by the Erasmus pro-
gram of the European Union. The authors thank Dr. Pierre
E. Rouviere (E.I. DuPont Company) for supporting this
project by the generous donation of six E. coli expression sys-
tems for BVMOs, and Prof. Margaret M. Kayser (University
of New Brunswick) for providing the strain for CPMOComa
.
[7] M. M. Kayser, G. Chen, J. D. Stewart, Synlett 1999,
153–158, and references cited therein.
[8] For a comprehensive review on biocatalytic desymmet-
rizations see: E. Garcia-Urdiales, I. Alfonso, V. Gotor,
Chem. Rev. 2005, 105, 313–354.
[9] a) I. Braun, F. Rudroff, M. D. Mihovilovic, T. Bach,
Angew. Chem. Int. Ed. 2006, 45, 5541–5543; b) M. D.
Mihovilovic, D. A. Bianchi, F. Rudroff, Chem.
Commun. 2006, 3214–3216; c) M. D. Mihovilovic, R.
References
[1] For general reviews on Baeyer–Villiger reactions see:
a) G.-J. Brink, I. W. C. E. Arends, R. A. Sheldon,
Chem. Rev. 2004, 104, 4105–4124; b) M. Renz, B. Meu-
nier, Eur. J. Org. Chem. 1999, 737–750; c) G. R. Krow,
Org. React. 1993, 43, 251–798.
Adv. Synth. Catal. 2007, 349, 1436 – 1444
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1443