Eight-membered ring construction by [4 + 2 + 2] annulation involving β-carbon elimination

Journal of the American Chemical Society

Volumn 128, Issue 7, 2006, Pages 2166-2167

  Murakami, Masahiro ^a   Ashida, Shinji ^a   Matsuda, Takanori ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

3 METHYL 3 PHENYLCYCLOBUTANONE; BICYCLO COMPOUND; CARBON; CYCLOBUTANONE DERIVATIVE; DIMETHYL 2,2 DI(BUT 2 YNYL)MALONATE; KETONE DERIVATIVE; TOLUENE; UNCLASSIFIED DRUG;

ANNULATION REACTION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; NUCLEAR OVERHAUSER EFFECT; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 33644559029     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0552895     Document Type: Article

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23. The reaction of the terminal diyne 1h under conditions B failed to afford product 31. Reaction of an internal diyne, deca-2,8-diyne, with 2b gave a complex mixture of products with both the Ni-phosphine and Ni-IPr catalysts, presumably due to ensuing double bond isomerization.
24. We assume the intermediates, such as A and B, which then undergo ring-opening through β-carbon elimination. Intermediate A would be more stable than B because intermediate B would suffer from unfavorable steric repulsion between the methyl group at the alkyne terminus and the ligand (L).