메뉴 건너뛰기




Volumn 75, Issue 1, 2010, Pages 16-29

Perylenequinone natural products: Enantioselective synthesis of the oxidized pentacyclic core

Author keywords

[No Author keywords available]

Indexed keywords

ASYMMETRIC SYNTHESIS; BINAPHTHALENES; CHEMICAL EQUATIONS; ENANTIOSELECTIVE; ENANTIOSELECTIVE APPROACH; ENANTIOSELECTIVE SYNTHESIS; HELICAL AXIS; KEY ELEMENTS; NATURAL PRODUCTS; STEREOGENIC CENTERS;

EID: 73449111924     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9013832     Document Type: Article
Times cited : (36)

References (67)
  • 4
    • 73449098382 scopus 로고    scopus 로고
    • 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.
  • 9
    • 27444432150 scopus 로고    scopus 로고
    • and references cited therein. For a review, see
    • For a review, see: Daub, M. E.; Herrero, S.; Chung, K.-R. FEMS Microbiol. Lett. 2005, 252, 197-206. and references cited therein.
    • (2005) FEMS Microbiol. Lett , vol.252 , pp. 197-206
    • Daub, M.E.1    Herrero, S.2    Chung, K.-R.3
  • 11
    • 73449089295 scopus 로고    scopus 로고
    • The chelation allows for keto-enol tautomerization; see ref 21
    • The chelation allows for keto-enol tautomerization; see ref 21.
  • 29
    • 37049089971 scopus 로고    scopus 로고
    • 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.
  • 37
    • 73449113876 scopus 로고    scopus 로고
    • 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.
  • 47
    • 73449142488 scopus 로고    scopus 로고
    • 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
    • 73449101323 scopus 로고    scopus 로고
    • 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 scopus 로고    scopus 로고
    • 1H NMR spectroscopy.
    • 1H NMR spectroscopy.
  • 54
    • 73449132097 scopus 로고    scopus 로고
    • 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.
  • 60
    • 0000437985 scopus 로고
    • (c) Green, K. J. Org. Chem. 1991, 56, 4325-4326.
    • (1991) J. Org. Chem , vol.56 , pp. 4325-4326
    • Green, K.1
  • 63
    • 73449112153 scopus 로고    scopus 로고
    • 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.
  • 65
    • 73449130705 scopus 로고    scopus 로고
    • 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
    • 73449142488 scopus 로고    scopus 로고
    • 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
    • 73449116592 scopus 로고    scopus 로고
    • 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.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.