Ruthenium- and palladium-catalyzed enyne cycloisomerizations: Differentially stereoselective syntheses of bicyclic structures

Journal of the American Chemical Society

Volumn 130, Issue 48, 2008, Pages 16176-16177

  Trost, Barry M ^a   Ferreira, Eric M ^a   Gutierrez, Alicia C ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; PALLADIUM; RUTHENIUM;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; COMPLEX FORMATION; DIASTEREOISOMER; ISOMERIZATION; QUANTUM YIELD; STEREOCHEMISTRY; SYNTHESIS; TEMPERATURE;

BICYCLO COMPOUNDS, HETEROCYCLIC; CATALYSIS; CYCLIZATION; MOLECULAR STRUCTURE; PALLADIUM; RUTHENIUM; STEREOISOMERISM;

EID: 57149106130     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8078835     Document Type: Article

References (11)

1. Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1985, 107, 1781-1783.
2. For reviews on enyne cycloisomerizations, see: (a) Trost, B. M.; Krische, M. J. Synlett 1998, 1-16.
3. (b) Michelet, V.; Toullec, P. Y.; Genêt, J.-P. Angew. Chem., Int. Ed. 2008, 47, 4268-4315.
4. Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 2002, 124, 5025-5036.
5. Recently, Fürstner et al. have described iron-catalyzed stereoselective enyne cycloisomerizations to form either cis- or trans-fused bicycles depending on the nature of the bicycle. See: Fürstner, A.; Majima, K.; Martín, R.; Krause, H.; Kattnig, E.; Goddard, R.; Lehmann, C. W. J. Am. Chem. Soc. 2008, 130, 1992-2004.
6. Relative configuration was determined by NOE experiments. See Supporting Information for details.
7. (a) Trost, B. M.; Tanoury, G. J.; Lautens, M.; Chan, C.; MacPherson, D. T. J. Am. Chem. Soc. 1994, 116, 4255-4267.
8. (b) Trost, B. M.; Romero, D. L.; Rise, F. J. Am. Chem. Soc. 1994, 116, 4268-4278.
9. (c) Trost, B. M.; Li, Y. J. Am. Chem. Soc. 1996, 118, 6625-6633.
10. This phenomenon is frequently seen in analogous palladium-catalyzed intramolecular Heck reactions of cyclic olefins and is generally suppressed by the addition of silver or thallium salts. These salts were ineffective as additives here. See: Link, J. T. Org. React. 2002, 60, 157-534.
11. The carboxylic acid moiety is likely exchanging with the formate ligand of the palladium complex, which is potentially preventing the olefin insertion from occurring. In entry 10, the highly coordinative nature of the ynamide functional group may be preventing the reaction from proceeding.