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73449098382
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This class also includes some partially reduced compounds from the molds of Alternaria and Stemphylium
-
This class also includes some partially reduced compounds from the molds of Alternaria and Stemphylium.
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6
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37049135466
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27444432150
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73449089295
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The chelation allows for keto-enol tautomerization; see ref 21
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The chelation allows for keto-enol tautomerization; see ref 21.
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13
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29
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37049089971
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The proposed structure of 22 is the keto-enol tautomer of the mold perylenequinones seen in Figure 2, with the exception of hypomycin B, 15. The perylenequinones actually exist as a mixture of the two tautomers, though the predominance of each tautomeric form is different for each natural product: Arnone, A.; Merlini, L.; Mondelli, R.; Nasini, G.; Ragg, E.; Scaglioni, L.; Weiss, U. J. Chem. Soc., Perkin Trans. 2 1993, 1447-1454.
-
The proposed structure of 22 is the keto-enol tautomer of the mold perylenequinones seen in Figure 2, with the exception of hypomycin B, 15. The perylenequinones actually exist as a mixture of the two tautomers, though the predominance of each tautomeric form is different for each natural product: Arnone, A.; Merlini, L.; Mondelli, R.; Nasini, G.; Ragg, E.; Scaglioni, L.; Weiss, U. J. Chem. Soc., Perkin Trans. 2 1993, 1447-1454.
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For a preliminary communication of this work, see
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For a preliminary communication of this work, see: Mulrooney, C. A.; Li, X.; DiVirgilio, E. S.; Kozlowski, M. C. J. Am. Chem. Soc. 2003, 125, 6856-6857.
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Li, X.2
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Kozlowski, M.C.4
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37
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73449113876
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In prior work, Zhang (ref 12) and Lown (ref 13) have shown similar transformations in the racemic syntheses of perylenequinones. Hauser (ref 15) also utilized dimerization of an o-quinone but found the pathway from the bis-o-quinone to the perylenequinone to be unproductive.
-
In prior work, Zhang (ref 12) and Lown (ref 13) have shown similar transformations in the racemic syntheses of perylenequinones. Hauser (ref 15) also utilized dimerization of an o-quinone but found the pathway from the bis-o-quinone to the perylenequinone to be unproductive.
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37049093828
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51949110789
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47
-
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73449142488
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Further investigations of the biaryl coupling reaction are examined in the subsequent paper in this series. Morgan, B. J, Mulrooney, C.A, O'Brien, E. M, Kozlowski, M. C. J. Org. Chem. 2010, 75, DOI 10.1021/jo901384h
-
Further investigations of the biaryl coupling reaction are examined in the subsequent paper in this series. Morgan, B. J.; Mulrooney, C.A.; O'Brien, E. M.; Kozlowski, M. C. J. Org. Chem. 2010, 75, (DOI 10.1021/jo901384h).
-
-
-
-
48
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-
73449101323
-
-
In a later synthesis involving substrate 52d, wet DMF is used as the solvent. These conditions cleave the acetates (presumably due to NaOH formed from trace H2O combined with the NaH) revealing a tetraphenol, which is exhaustively alkylated with the MeI to form a tetramethyl ether 82, Scheme 18
-
2O combined with the NaH) revealing a tetraphenol, which is exhaustively alkylated with the MeI to form a tetramethyl ether (82, Scheme 18).
-
-
-
-
49
-
-
73449127441
-
-
1H NMR spectroscopy.
-
1H NMR spectroscopy.
-
-
-
-
54
-
-
73449132097
-
-
The dinaphthofuranedione 24 in Scheme 2 (ref 20) is also similar to the strained extended quinone structure of 69.
-
The dinaphthofuranedione 24 in Scheme 2 (ref 20) is also similar to the strained extended quinone structure of 69.
-
-
-
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56
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0001292049
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(b) Tapuhi, Y.; Kalisky, O.; Agranat, I. J. Org. Chem. 1979, 44, 1949-1952.
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Kita, Y.5
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63
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73449112153
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Improvements to the hydroxylation reaction were later developed, mitigating the loss of yield and enantioenrichment. As seen in the subsequent papers in this series on more complex intermediates, no erosion of enantioenrichment was observed when NaOAc was used to quench the reagents after oxidation. The NaOAc was added prior to solvent evaporation and subsequent NaOH treatment removes excess oxidant and TFA that can cause degradation
-
Improvements to the hydroxylation reaction were later developed, mitigating the loss of yield and enantioenrichment. As seen in the subsequent papers in this series on more complex intermediates, no erosion of enantioenrichment was observed when NaOAc was used to quench the reagents after oxidation. The NaOAc was added prior to solvent evaporation and subsequent NaOH treatment removes excess oxidant and TFA that can cause degradation.
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64
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34547152046
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Dickstein, J. S.; Mulrooney, C. A.; O'Brien, E. M; Morgan, B. J.; Kozlowski, M. C. Org. Lett. 2007, 9, 2441-2444.
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Dickstein, J.S.1
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Morgan, B.J.4
Kozlowski, M.C.5
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65
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73449130705
-
-
Merlic, in ref 17, synthesized perylenequinone 39 as the racemate via the dimerization of an o-quinone, but no logical entry to the enantioenriched variant is available with such a route.
-
Merlic, in ref 17, synthesized perylenequinone 39 as the racemate via the dimerization of an o-quinone, but no logical entry to the enantioenriched variant is available with such a route.
-
-
-
-
66
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73449142488
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Following this work, the synthesis of 39 evolved further, culminating in a 16-step protocol with 4.2% overall yield of 98% ee material. The evolution is described briefly in ref 19 and in detail in the third paper in this series. Morgan, B. J.; Mulrooney, C.; Kozlowski, M. C. J. Org. Chem. 2010, 75 (DOI 10.1021/jo9013854).
-
Following this work, the synthesis of 39 evolved further, culminating in a 16-step protocol with 4.2% overall yield of 98% ee material. The evolution is described briefly in ref 19 and in detail in the third paper in this series. Morgan, B. J.; Mulrooney, C.; Kozlowski, M. C. J. Org. Chem. 2010, 75 (DOI 10.1021/jo9013854).
-
-
-
-
67
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73449116592
-
-
The high wavenumber of the C=O in the acetate groups has been observed in simple acetate protected phenols: The Aldrich Library of 13C and 1H FTNMR Spectra, 1st ed.; Pouchert, C. J., Behnke, J., Eds.; Aldrich Chemical Co.: Milwaukee, WI, 1993.
-
The high wavenumber of the C=O in the acetate groups has been observed in simple acetate protected phenols: The Aldrich Library of 13C and 1H FTNMR Spectra, 1st ed.; Pouchert, C. J., Behnke, J., Eds.; Aldrich Chemical Co.: Milwaukee, WI, 1993.
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