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(b). Makarieva, T. N.; Guzii, A. G.; Denisenko, V. A.; Dmitrenok, P. S.; Santalova, E. A; Pokanevich, E. V.; Molinski, T. F.; Stonik, V. A. J. Nat. Prod. 2005, 68, 255-257.
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56549128555
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Tsukamoto, S.; Takeuchi, T.; Rotinsulu, H.; Mangindaan, R. E. P.; van Soest, R. W. M.; Ukai, K.; Kobayashi, H.; Namikoshi, M.; Ohta, T.; Yokosawa, H. Bioorg. Med. Chem. Lett. 2008, 78, 6319-6320.
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14
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84868927760
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Also implicit in the logic of their deduction is that leucettamols must be chiral-and racemic-because both ends of each molecule have the same configuration and that the positions of the skipped olefins in the long chains make them constitutionally unsymmetrical, but the molecules would still be chiral even if they were constitutionally symmetrical (with the exception of the meso form, in which each end has the same relative configuration but with mirror image absolute configurations; see text and Figure 1 for further discussion, Comparison of the rotation of C28 rhizochalin aglycone (4a,[α]D +11, ref 2a) with the zero specific rotation observed for 1 and 2 is also invoked to further support the conclusion that both leucettamols are racemic; however as we have shown elsewhere ref 2c, the former molecule represents a pseudo-C 2 molecule that is fully expected to be chiral, regardless o
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2 molecule that is fully expected to be chiral, regardless of the presence of the near mid-chain keto group.
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16
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0002171949
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(b). Kawai, M.; Nagai, U.; Katsumi, M. Tetrahedron Lett. 1975, 76, 3165-3166.
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Kawai, M.1
Nagai, U.2
Katsumi, M.3
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18
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0030181798
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Kawamura, A.; Berova, N.; Dirsch, V.; Mangoni, A.; Nakanishi, K.; Schwartz, G.; Bielawska, A.; Hannun, Y.; Kitagawa, I. Bioorg. Med. Chem. 1996, 4, 1035-1043.
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Kawamura, A.1
Berova, N.2
Dirsch, V.3
Mangoni, A.4
Nakanishi, K.5
Schwartz, G.6
Bielawska, A.7
Hannun, Y.8
Kitagawa, I.9
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19
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10044237683
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Kossuga, M. H.; MacMillan, J. B.; Rogers, E. W.; Molinski, T. F.; Nascimento, G. S. F.; Rocha, R. M.; Berlinck, R. G. S. J. Nat. Prod. 2004, 67, 1879-1881.
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MacMillan, J.B.2
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Nascimento, G.S.F.5
Rocha, R.M.6
Berlinck, R.G.S.7
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65249175173
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No leucettamol B (2) was detected in these extracts.
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No leucettamol B (2) was detected in these extracts.
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21
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33748238501
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Ikemoto, N.; Lo, L.-C.; Nakanishi, K. Angew. Chem., Int. Ed. 1992, 37, 890-891.
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Angew. Chem., Int. Ed
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Ikemoto, N.1
Lo, L.-C.2
Nakanishi, K.3
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22
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65249144604
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Although the hydrogenation product 11 of leucettamol A (1, was revealed to be a constitutional C2 dimer, the assignment of configuration in 1 would have been made more complicated if it were C1 because of the need to place each inequivalent end group at correct ends of the unsymmetrical skipped polyene chain. Herein lies a limitation to the CD method. However the correct assignment could still be made by 2D NMR spin correlation (e.g, TOCSY, HMBC) of the compound prepared by per-benzoylation of 1 without hydrogenation and using the empirical NH chemical shift method described in the text to identify threo and erythro end groups
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1 because of the need to place each inequivalent end group at correct ends of the unsymmetrical skipped polyene chain. Herein lies a limitation to the CD method. However the correct assignment could still be made by 2D NMR spin correlation (e.g., TOCSY, HMBC) of the compound prepared by per-benzoylation of 1 without hydrogenation and using the empirical NH chemical shift method described in the text to identify threo and erythro end groups.
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65249190318
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In our opinion, the (CO)NH 1H NMR chemical shift in CDCl3 only is more reliable for assignment of relative configuration, in most cases, than measurements of vicinal couplings or NOEs in the corresponding cyclic oxazolidinone1 or thiazolidinone derivatives
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1H NMR chemical shift in CDCl3 only is more reliable for assignment of relative configuration, in most cases, than measurements of vicinal couplings or NOEs in the corresponding cyclic oxazolidinone1 or thiazolidinone derivatives.
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24
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65249134081
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In the text of the paper ref 1, the authors state, apparently in contradiction to their depicted structure, that 1 has, threo stereochemistry at both ends of the molecule. This appears to be a typographical error since the 1H NMR data support the all-erythro configuration for leucettamol A as shown
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1H NMR data support the all-erythro configuration for leucettamol A as shown.
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25
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65249092044
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Leucettamol B (2) is also an expected product of oxidation of 1 by a singlet oxygen ene-reaction followed by disproportionation of the resultant hydroperoxide i and may possibly be an artifact.
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Leucettamol B (2) is also an expected product of oxidation of 1 by a singlet oxygen ene-reaction followed by disproportionation of the resultant hydroperoxide i and may possibly be an artifact.
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26
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84868936303
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D 0(c 1.26, MeOH), gives α=-0.0478 in a 10 cm cell or α=-0.00478 ina1cmcell. The latter value is close to the limit of detection (twice the S/N) of older model polarimeters.
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D 0(c 1.26, MeOH), gives α=-0.0478 in a 10 cm cell or α=-0.00478 ina1cmcell. The latter value is close to the "limit of detection" (twice the S/N) of older model polarimeters.
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27
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0028364176
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D-11.2 (c 10, pyridine), Combined Chemical Dictionary; Taylor and Francis, 2008, http://www.chemnetbase.com/.
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D-11.2 (c 10, pyridine), Combined Chemical Dictionary; Taylor and Francis, 2008, http://www.chemnetbase.com/.
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0032958221
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Li, S.; Wilson, W. K.; Schroepfer, G. J. J. Lipid Res. 1999, 40, 764-772.
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Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-651.
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Zhao, N.1
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Nakanishi, K.4
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34
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84868927758
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We have not been able to detect second-order effects of the CD spectra of perbenzoyl DSs due to intramolecular π-π stacking under the conditions of measurement. Such effects are either too weak to observe or averaged out by dynamical behavior under the conditions of the measurements c ≈ 10 -4-10-5 M, 23 °C, MeOH or CH3CN
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3CN).
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36
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0025312059
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(a). Horton, P.; Inman, W. D.; Crews, P. J. Nat. Prod. 1990, 53, 143-151.
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Gerngross, O.1
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