Whole-cell Mediated Baeyer-Villiger Oxidation of Functionalized Bicyclo[3.3.0]ketones by Recombinant E. coli

Marko D. Mihovilovic; Bernhard Müller; Margaret M. Kayser; Jon D. Stewart; Peter Stanetty

doi:10.1055/s-2002-25341

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Synlett 2002(5): 0703-0706
DOI: 10.1055/s-2002-25341

LETTER

Whole-cell Mediated Baeyer-Villiger Oxidation of Functionalized Bicyclo[3.3.0]ketones by Recombinant E. coli

Marko D. Mihovilovic*^a, Bernhard Müller^a, Margaret M. Kayser^b, Jon D. Stewart^c, Peter Stanetty^a
^a Vienna University of Technology, Institute of Applied Synthetic Chemistry, Getreidemarkt 9/163-OC, 1060 Vienna, Austria
Fax: +43(1)5880115499; e-Mail: mmihovil@pop.tuwien.ac.at;
^b University of New Brunswick, Department Physical Sciences, Saint John, N.B., E2L 4L5, Canada
^c University of Florida, Department Chemistry, Gainesville, FL 32611, USA

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Publication History

Received 27 February 2002
Publication Date:
07 February 2007 (online)

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Abstract

Recombinant whole cells of Escherichia coli overexpressing Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (E.C. 1.14.13.22) have been utilized for the Baeyer-Villiger oxidation of functionalized bicyclo[3.3.0]ketones. Prochiral substrates were designed to probe the impact of polarity and spatial configuration of the functional groups on conversion and enantioselectivity. The data give additional insight into the steric requirements of the active site of the enzyme for high optical purity. The synthetic utility of the engineered E. coli strain is demonstrated and contributions to the non-natural substrate profile available so far are provided.

Key words

biocatalysis - recombinant whole-cell biotransformation - cyclohexanone monooxygenase - Baeyer-Villiger oxidation - substrate profiling - enantioselectivity

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49

Physical and spectroscopic data of lactones 2:
4a S-cis -Hexahydro-cyclopenta[ c ]pyran-3(1 H )-one(2a). Colorless oil; ¹H NMR (200 MHz, CDCl₃): δ = 1.20-2.08 (m, 6 H), 2.25-2.69 (m, 4 H), 4.00 (dd, J = 7 Hz, J = 20 Hz, 1 H), 4.37 (dd, J = 7 Hz, J = 20 Hz, 1 H); ¹³C NMR (50 MHz, CDCl₃): δ = 25.0 (t), 28.9 (t), 34.2 (t), 34.3 (t), 34.4 (d), 36.3 (d), 67.4 (t), 173.4 (s).
4a S- (4aα,6β,7aα)-Hexahydro-6-methoxy-cyclopenta [ c ]pyran-3(1 H )-one(2b). Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.50-1.65 (m, 2 H), 1.82-2.10 (m, 2 H),
2.40-2.65 (m, 4 H), 3.23 (s, 3 H), 3.72-3.83 (m, 1 H, H6), 4.08 (dd, J = 14 Hz, J = 7 Hz, 1 H), 4.31 (dd, J = 14 Hz, J = 7 Hz, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 32.8 (d), 33.8 (t), 34.9 (t), 35.2 (d), 38.0 (t), 56.4 (q), 69.9 (t), 82.3 (d), 173.8 (s).
4a S- (4aα,6α,7aα)-Hexahydro-6-methoxy-cyclopenta [ c ]pyran-3(1 H )-one(2c). Colorless oil; ¹H NMR (400 MHz, CDCl₃): δ = 1.24-1.44 (m, 1 H), 1.52-1.68 (m, 1 H),
2.00-2.90 (m, 6 H), 3.29 (s, 3 H), 3.80-3.92 (m, 1 H), 4.10 (dd, J = 14 Hz, J = 7 Hz, 1 H), 4.35 (dd, J = 14 Hz, J = 7 Hz, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 32.1 (d), 34.1 (t), 34.2 (t), 34.4 (d), 38.4 (t), 55.7 (q), 69.7 (t), 81.4 (d), 173.6 (s).
4a R- (4aα,6β,7aα)-6-Chloro-hexahydro-cyclopenta [ c ]pyran-3(1 H )-one(2d). Colorless crystals, mp 90-92 °C; ¹H NMR (400 MHz, CDCl₃): δ = 1.58-1.68 (m, 1 H),
1.70-1.81 (m, 1 H), 2.30-2.70 (m, 6 H), 4.05-4.15 (m, 1 H), 4.20-4.30 (m, 2 H); ¹³C NMR (100 MHz, CDCl₃): δ = 32.8 (d), 34.2 (t), 35.1 (d), 38.8 (t), 43.1 (t), 56.6 (d), 69.2 (t), 172.7 (s).
4a R- (4aα,6α,7aα)-6-Chloro-hexahydro-cyclopenta [ c ]pyran-3(1 H )-one(2e). Colorless crystals, mp 88-90 °C; ¹H NMR (400 MHz, CDCl₃): δ = 1.60-1.80 (m, 1 H), 1.92-2.10 (m, 1 H), 2.20-2.50 (m, 3 H), 2.65-3.20 (m, 3 H), 4.10 (dd, J = 14 Hz, J = 7 Hz, 1 H), 4.45-4.55 (m, 1 H); ¹³C NMR (100 MHz, CDCl₃): δ = 32.2 (d), 33.7 (t), 34.5 (d), 39.5 (t), 43.5 (t), 61.4 (d), 69.1 (t), 172.8 (s).