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Volumn 15, Issue 44, 2009, Pages 11837-11841

Gold(I)-catalyzed synthesis of highly substituted 2-cyclopentenones from 5-siloxypent-3-en-1-ynes

Author keywords

Carboalkoxylation; Cyclopentenone; Gold; Homogeneous catalysis; Quaternary carbon

Indexed keywords

CARBOALKOXYLATION; CYCLOPENTENONE; CYCLOPENTENONES; HOMOGENEOUS CATALYSIS; QUATERNARY CARBON;

EID: 73249139585     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200901824     Document Type: Article
Times cited : (24)

References (54)
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    • As observed in the previous study for the siloxycyclization-[3,3]- sigmatropic pathway of 3-siloxy-1,6-enynes, the reaction gave no silyl ether 5a, even in the absence of any alcohol additives.(a)For the detailed procedure for the synthesis of the substrates, see the Supporting Information;(b) we also tried to investigate the reactivity of 5-methoxypent-3-en-yne derivative of 8. However, all our efforts to prepare the 5-methoxy-3-en-1-ynes from the corresponding alcohols proved troublesome, because of the poor stability of the corresponding alcohols under the reaction condition. The reaction conditions investigated include; (i) NaH/MeI in THF or DMF; ii) Ag2O/MeI in various solvents; iii) CH3OC=NHCCl3 with various Lewis acids.
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    • (a)Using other solvents (CH3CN, THF, EtOAc) significantly decreased the yield of the reaction; (b)we also examined various trialkylsilyl ethers: trimethylsilyl ethers provided the target in somewhat smaller yield, while triisopropylsilyl ethers significantly dropped the yield.
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    • (a)The reaction performed in the presence of HF (up to 1 equiv) gave led to the complete decomposition of the starting material with no indication of the product formation; (b)the catalytic reaction under aerobic conditions (open flask condition) gave comparable results to the reactions under N2 atmosphere;(c)the reaction of the corresponding alcohol led to decomposition of the staring material with no indication of the product formation; also, we found out that the TES silyl ethers of tertiary alcohols are stable in general under the reaction condition-based on these experiments, alternative explanation on the cyclopentenone formation promoted by the initial desilylation and the subsequent cyclization can be reasonably excluded; (d) it should be noted that the scope of the reaction was strictly limited to the terminal alkynes; reaction of internal alkynes led to the decomposition of the staring material with no indication of formation of the cyclopentenones.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.