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35349007961
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The preceding article by Miller, Yu, and Allemann reports the enzymatic cydization of 2-fluorofarnesyl PP to 5-fluorogermacrene A with recombinant aristolochene synthase from Penicillium roqueforti.
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The preceding article by Miller, Yu, and Allemann reports the enzymatic cydization of 2-fluorofarnesyl PP to 5-fluorogermacrene A with recombinant aristolochene synthase from Penicillium roqueforti.
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35349016830
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1H NMR signals.
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1H NMR signals.
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41
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0000028063
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The conformations of flexible germacrenes are denoted as UU, DD, UD and DU. U (up) and D (down) refer to the orientations of C14 and C15 methyl groups; a) J. K. Sutherland, Tetrahedron 1974, 30, 1651-1660;
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The conformations of flexible germacrenes are denoted as UU, DD, UD and DU. U (up) and D (down) refer to the orientations of C14 and C15 methyl groups; a) J. K. Sutherland, Tetrahedron 1974, 30, 1651-1660;
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43
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35348997398
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(+)-Germacrene A behaves in solution (25°C) as a 5:3:2 mixture of UU, UD, and DU conformers, respectively. See ref. [24].
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(+)-Germacrene A behaves in solution (25°C) as a 5:3:2 mixture of UU, UD, and DU conformers, respectively. See ref. [24].
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-
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44
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3042988525
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-1) of the four possible conformers of 1-fluorogermacrene A calculated by the Allinger MM2 force-field method were as follows: UU (0.00, UD (0.55, DD (1.85, and DU 1.96
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-1) of the four possible conformers of 1-fluorogermacrene A calculated by the Allinger MM2 force-field method were as follows: UU (0.00), UD (0.55), DD (1.85), and DU (1.96).
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49
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35348930471
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In the absence of any independent evidence concerning the enantiomeric purity and absolute configuration of the, )-1-fluorogermacrene A product, we assume that the fluoro analogue has the same 7R stereochemistry of the isopropenyl group as 5-epi-aristolochene 4, since both are produced by TEAS with comparable catalytic efficiencies
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In the absence of any independent evidence concerning the enantiomeric purity and absolute configuration of the (-)-1-fluorogermacrene A product, we assume that the fluoro analogue has the same 7R stereochemistry of the isopropenyl group as 5-epi-aristolochene (4), since both are produced by TEAS with comparable catalytic efficiencies.
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50
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0030796451
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X-ray analysis of the structure of TEAS in combination with studies regarding the catalytic properties of a TEAS mutant suggests that Tyr520 participates as an active-site acid that protonates, -germacrene A. See C. M. Starks, K. Back, J. Chappell, J. P. Noel, Science 1997, 277, 1815-1820 and ref, 3
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X-ray analysis of the structure of TEAS in combination with studies regarding the catalytic properties of a TEAS mutant suggests that Tyr520 participates as an active-site acid that protonates (+)-germacrene A. See C. M. Starks, K. Back, J. Chappell, J. P. Noel, Science 1997, 277, 1815-1820 and ref. [3].
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60
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35348995432
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Evidence supporting germacrene A as a neutral intermediate in TEAS and aristolochene synthase catalysis has been provided by Chappell,[3] Allemann,[4a] and Cane[4b] through site-directed mutagenesis
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[4b] through site-directed mutagenesis.
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