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Volumn 132, Issue 14, 2010, Pages 5030-5032

Enantioselective thiourea-catalyzed cationic polycyclizations

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUNDS; CATALYSTS; THIOUREAS;

EID: 77950805314     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja101256v     Document Type: Article
Times cited : (269)

References (64)
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    • Note
    • The analogous urea catalysts are less reactive but induce only slightly lower levels of enantioselectivity (85% ee for the urea analogue of catalyst 8 in the cyclization of 1 to 2). The sulfur atom of the thiourea therefore does not appear to play a direct role in the reaction mechanism.
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    • In the absence of the thiourea catalyst, an HCl-catalyzed process forms a monocyclized byproduct.
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    • Higher yields and faster reactions are observed using increasing amounts of HCl, though with diminished enantioselectivities.
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    • Note
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    • Preliminary 2° KIE studies indicate that ionization of the chlorolactam is rate-limiting in these reactions. As the enantioselectivity- determining cyclization step occurs after the rate-determining step, the question of whether enantioselectivity is achieved by stabilizing or destabilizing interactions cannot be addressed by absolute rate comparisons of the different catalysts.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.