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Volumn 130, Issue 48, 2008, Pages 16417-16423

Gold-catalyzed deoxygenative Nazarov cyclization of 2,4-dien-1-als for stereoselective synthesis of highly substituted cyclopentenes

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; COMPLEXATION; CYCLIZATION; GOLD; HYDROCARBONS; HYDROGEN; OLEFINS; OXYGEN; REACTION KINETICS; STEREOCHEMISTRY; STEREOSELECTIVITY; STRUCTURAL ANALYSIS; SULFUR;

EID: 57149091342     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja806415t     Document Type: Article
Times cited : (84)

References (78)
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    • Addition of a C=O bond to π-alkynes: (a) Asao, N.; Aikawa, H.; Yamamoto, Y. J. Am. Chem. Soc. 2004, 126, 7458.
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    • Double nucleophilic additions to 1,3-dienes or 1,4-diacetyl-2-alkenes were reported for Pd(II), Pd(0) or Ga(III) catalysts, but these examples did not involve a cyclization of starting substrates. See: (a) Jonasson, C.; Roon, M.; Backvall, J.-E. J. Org. Chem. 2000, 65, 2122.
    • Double nucleophilic additions to 1,3-dienes or 1,4-diacetyl-2-alkenes were reported for Pd(II), Pd(0) or Ga(III) catalysts, but these examples did not involve a cyclization of starting substrates. See: (a) Jonasson, C.; Roon, M.; Backvall, J.-E. J. Org. Chem. 2000, 65, 2122.
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    • 16b In this study, we obtain evidence for Nazarov cyclization for one class of annulation using cationic gold catalyst (Table 2 and Scheme 10). Since the other cyclizations share the same initial step, Nazarov cyclization is likely involved therein.
    • 16b In this study, we obtain evidence for Nazarov cyclization for one class of annulation using cationic gold catalyst (Table 2 and Scheme 10). Since the other cyclizations share the same initial step, Nazarov cyclization is likely involved therein.
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    • Treatment of allylSiMe3 and PPh3AuSbF6 did not generate PPh3Au(allyl) species through an allyl exchange; see ref 9c
    • 3Au(allyl) species through an allyl exchange; see ref 9c.
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    • 6 (3 mol %) gave 1,4-dimethoxycyclopentyl product in satisfactory yield (88%) among these acidic catalysts. For detailed information, see Table S2 in Supporting Information.
    • 6 (3 mol %) gave 1,4-dimethoxycyclopentyl product in satisfactory yield (88%) among these acidic catalysts. For detailed information, see Table S2 in Supporting Information.
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    • 1H NOE spectra, which are provided in Supporting Information.
    • 1H NOE spectra, which are provided in Supporting Information.
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    • Formation of the [4 + 2]-annulated product 4e from cis-dienal is proposed to follow the mechanism below. The key step involves an metal exchange between allylic cation and 2-siloxymethylallylsilane to give cation A″ and Au(I)-alkoxy species. This Au(I)-alkoxy species is highly nucleophilic to undergo nucleophilic addition to form species C″, and ultimately forms observed cycloadduct 4e.
    • Formation of the [4 + 2]-annulated product 4e from cis-dienal is proposed to follow the mechanism below. The key step involves an metal exchange between allylic cation and 2-siloxymethylallylsilane to give cation A″ and Au(I)-alkoxy species. This Au(I)-alkoxy species is highly nucleophilic to undergo nucleophilic addition to form species C″, and ultimately forms observed cycloadduct 4e.
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    • The annulated compounds 4b, 4c, 4f, and 4g were obtained as minor products according to the mechanism below.
    • The annulated compounds 4b, 4c, 4f, and 4g were obtained as minor products according to the mechanism below.
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    • 18O-enriched 1b and 6b are provided in Supporting Information.
    • 18O-enriched 1b and 6b are provided in Supporting Information.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.