Ru-catalyzed cyclization of terminal alkynals to cycloalkenes

Journal of the American Chemical Society

Volumn 128, Issue 30, 2006, Pages 9576-9577

  Varela, Jesús A ^a   González Rodríguez, Carlos ^a   Rubín, Silvia G ^a   Castedo, Luis ^a   Saá, Carlos ^a  

^a UNIVERSITY OF SANTIAGO DE COMPOSTELA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; CARBON; CYCLOALKENE; RUTHENIUM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CYCLIZATION; HEATING; ISOMERIZATION; REACTION ANALYSIS; REDUCTION; STRUCTURE ANALYSIS;

EID: 33746588234     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0610434     Document Type: Article

References (34)

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23. (a) Minor amounts of the isomer 3a (<5%) have been observed,
24. (b) See Supporting Information for more details and for other catalytic conditions.
25. 3) was also obtained in 30% yield.
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32. It has been suggested that Cp*Ru(cod)Cl, when heated with AcOH at 65 °C, forms a hydrido-Ru(IV) complex that upon coordination with alkynes gives a vinyl-Ru species. Le Paih, J.; Cuervo, D.; Dérien, S.; Dixneuf, P. H. Synlett 2000, 1, 95. We observed no products suggestive of this process.
33. Reductive elimination products derived from intermediates II (vinyl acetate IIa) or III (aldehyde 11a) did not afford the observed cycloalkene 2a after heating their solutions in AcOH at 90 °C in the presence of the Ru catalyst. See Supporting Information S5 for details.
34. The isomeric cycloalkenes 3 probably arise through isomerization of the Ru hydride IV.