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Volumn 47, Issue 2, 2008, Pages 346-349

Platinum-catalyzed formation of cyclic-ketone-fused indoles from N-(2-alkynylphenyl)lactams

Author keywords

Carbenes; Homogeneous catalysis; Insertion; Platinum; Rearrangement

Indexed keywords

AMIDES; CATALYSIS; CYCLIZATION; MOLECULAR INTERACTIONS; PLATINUM;

EID: 38049072099     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200702931     Document Type: Article
Times cited : (144)

References (54)
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    • 1H NMR spectrum of the mixture, as well as the signal at δ = 4.14 ppm expected for the benzylic hydrogen atoms.
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    • This structural assignment is supported by the isolation and characterization of the side product from the reaction of lactam 7a, in which a methyl group is at the alkyne terminus
    • This structural assignment is supported by the isolation and characterization of the side product from the reaction of lactam 7a, in which a methyl group is at the alkyne terminus.
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    • The reason for this decreased reactivity is not clear, but the molecular sieves may affect the Pt catalyst and partially trap the reactive acylium intermediate
    • The reason for this decreased reactivity is not clear, but the molecular sieves may affect the Pt catalyst and partially trap the reactive acylium intermediate.
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    • The structure of the chloride derivative was assigned on the basis of the close resemblance of the signals in its NMR spectra to those of the bromide product as well as the characteristic isotope pattern in its ESI+ mass spectrum
    • + mass spectrum.
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    • Additional evidence for the existence of the acylium intermediate C and/or the preceding spiro-zwitterionic intermediate is the formation of the ethyl ester of acid 6 in 30% yield along with the product 4 (45% yield) when EtOH (1.5 equiv) was added to the reaction mixture to trap the intermediates. Moreover, when EtOH (at reflux) was used as the solvent, the ethyl ester was isolated in 68% yield, and the product 4 was observed (< 2%).
    • Additional evidence for the existence of the acylium intermediate C and/or the preceding spiro-zwitterionic intermediate is the formation of the ethyl ester of acid 6 in 30% yield along with the product 4 (45% yield) when EtOH (1.5 equiv) was added to the reaction mixture to trap the intermediates. Moreover, when EtOH (at reflux) was used as the solvent, the ethyl ester was isolated in 68% yield, and the product 4 was observed (< 2%).
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    • This result also suggests that the evolution of the Pt carbenoid D may not be the rate-limiting step, which would explain why substrates 7 with a primary alkyl group at the alkyne terminus reacted faster than those with an aryl group, although aryl groups usually show greater aptitude for nucleophilic migration
    • This result also suggests that the evolution of the Pt carbenoid D may not be the rate-limiting step, which would explain why substrates 7 with a primary alkyl group at the alkyne terminus reacted faster than those with an aryl group, although aryl groups usually show greater aptitude for nucleophilic migration.


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