Pt-catalyzed pentannulations from in situ generated metallo-carbenoids utilizing propargylic esters

Journal of the American Chemical Society

Volumn 127, Issue 36, 2005, Pages 12468-12469

  Bhanu Prasad, B A ^a   Yoshimoto, Francis K ^a   Sarpong, Richmond ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENOID; ESTER DERIVATIVE; METAL COMPLEX; METAL DERIVATIVE; PLATINUM; RUTHENIUM;

ARTICLE; CATALYSIS; COMPLEX FORMATION; HIGH TEMPERATURE; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS;

ALKYNES; CATALYSIS; CYCLIZATION; ESTERS; MOLECULAR STRUCTURE; ORGANOPLATINUM COMPOUNDS; PLATINUM;

EID: 24744464788     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja053192c     Document Type: Article

References (26)

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7. The C-O bond cleavage may not be a required step as the product may be envisioned to arise directly from 2.
8. Propargylic esters as substrates to access carbenes and metallo-carbenoids have been previously proposed. See: (a) Frey, L. F.; Tillyer, R. D.; Ouellet, S. G.; Reamer, R. A.; Grabowski, E. J. J.; Reider, P. J. J. Am. Chem. Soc. 2000, 122, 1215-1216.
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15. Obtained as a 17:3 ratio of olefin isomers; major is shown. This mixture was saponified to give the β-ketoester exclusively (see Supporting Information).
16. Optimization and mechanistic studies of this transformation are underway.
17. For related precedent, see: Cariou, K.; Mainetti, E.; Fensterbank, L.; Malacria, M. Tetrahedron 2004, 60, 9745-9755.
18. 2, and NMO.
19. A single diastereomer, established by nOe to be that shown (see Supporting Information), was obtained.
20. Recently, an elegant study describing the synthesis of nonaromatic compounds related to eqs 1 and 2 was reported. See: Shi, X.; Gorin, D. J.; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 5802-5803. The insightful mechanistic hypothesis put forth in this account cannot be ruled out for the formation of 18, 21, or 22 and may also explain the formation of the other pentannulated products. However, the formation of 21b (via 23 and 24). for example, would require a seemingly unlikely isomerization of cyclopentadiene 21a to the diene 21b. (Diagram presented)
21. Propargylic ester substrates are readily converted under our reaction conditions in 1,2-DCE to the desired products, albeit in lower isolated yields compared to reactions performed in PhMe.
22. 2 and may even be more efficient. See: (a) Fürstner, A.; Stelzer, F.; Szillat, H. J. Am. Chem. Soc. 2001, 123, 11863-11864.
23. (b) Kobayashi, S.; Kakumoto, K.; Sugiura, M. Org. Lett. 2002, 4, 1319-1322.
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25. 3 outcompetes the alkyne substrate for open coordination sites on the metal center.
26. The oxidation state of the active Pt species is still under investigation.