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Volumn 132, Issue 14, 2010, Pages 5027-5029

Enantioselective polyene cyclization via organo-SOMO catalysis

Author keywords

[No Author keywords available]

Indexed keywords

ACIDIC CONDITIONS; ARYLATIONS; CARBOCYCLES; CASCADE MECHANISM; ELECTRON-RICH; ENAMINES; ENANTIOSELECTIVE; ENANTIOSELECTIVE FORMATION; ENANTIOSELECTIVE RADICALS; ORGANOCATALYTIC; POLYCYCLIZATION; POLYENALS; ROOM TEMPERATURE; SINGLE CATALYST; SINGLE ELECTRON OXIDATION; SINGLY OCCUPIED MOLECULAR ORBITALS;

EID: 77950849290     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja100185p     Document Type: Article
Times cited : (198)

References (61)
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    • For examples of enantioselective atom-transfer radical bicyclizations employing chiral Lewis acids, see
    • For examples of enantioselective atom-transfer radical bicyclizations employing chiral Lewis acids, see: Yang, D., Gu, S., Yan, Y.-L., Zhao, H.-W., and Zhu, N.-Y. Angew. Chem., Int. Ed. 2002, 41, 3014
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    • For reviews of catalytic enantioselective radical (cascade) reactions, see:
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    • This mechanism is in agreement with our previously described intramolecular α-arylation of aldehydes (see ref 9g)
    • This mechanism is in agreement with our previously described intramolecular α-arylation of aldehydes (see ref 9g).
  • 54
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    • Note
    • 2 (see ref 15a).
  • 55
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    • Note
    • Under the reaction conditions, alkene protonation followed by subsequent cationic cyclization is not a feasible process. Under typical cationic cyclization conditions (see ref 4d), cationic cyclization could be achieved in a separate step.
  • 56
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    • Note
    • Structural assignments of 8 and 13 as well as the absolute configuration of 8 (after chemical derivatization) were secured by X-ray crystallographic analysis (see the Supporting Information for details).
  • 58
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    • Note
    • 2 (0.500 mmol, 2.50 equiv), NaTFA (0.400 mmol, 2.00 equiv), and TFA (0.400 mmol, 2.00 equiv) in i -PrCN (1.0 mL) was slowly added over 7 h using a syringe pump at room temperature. After stirring had been continued for a further 17 h, the light-green solution was subjected to aqueous workup and purified by flash chromatography to afford the cyclization product.
  • 59
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    • Note
    • Further evidence against a radical polar crossover reaction mechanism was obtained by the examination of a mismatched tricyclization substrate consisting of two trisubstituted electron-rich alkene moieties: significantly lower reaction efficiency (25% yield of the desired tetracycle) and only partial conversion were observed.
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    • Note
    • We assume levels of enantiocontrol similar to those observed for 5 and 16.
  • 61
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    • Note
    • Estimated by semiempirical PM3 calculations on 17 using Gaussian 03.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.