Chemo- and regioselective dimerization of terminal alkynes promoted by methylaluminoxane

Organic Letters

Volumn 2, Issue 6, 2000, Pages 737-740

  Dash, Aswini K ^a   Eisen, Moris S ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000391747     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol9903584     Document Type: Article

References (38)

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28. Stockis and Hoffmann have performed calculations on the polarization of the π*-orbitals in TMSC≡CH. The electronic effects due to the polarization are believed to be responsible for the difference in regioselectivities of the dimerization results. Stockis, A.; Hoffmann, R. J. Am. Chem. Soc. 1980, 102, 2952. The cis isomer will probably be formed by an isomerization of the trans isomer via an envelope mechanism; see: Wang, J. Q.; Dash, A. K.; Berthet, J. C.; Ephritikhine, M.; Eisen, M. S. Organometallics 1999, 18, 2407.
29. Stockis and Hoffmann have performed calculations on the polarization of the π*-orbitals in TMSC≡CH. The electronic effects due to the polarization are believed to be responsible for the difference in regioselectivities of the dimerization results. Stockis, A.; Hoffmann, R. J. Am. Chem. Soc. 1980, 102, 2952. The cis isomer will probably be formed by an isomerization of the trans isomer via an envelope mechanism; see: Wang, J. Q.; Dash, A. K.; Berthet, J. C.; Ephritikhine, M.; Eisen, M. S. Organometallics 1999, 18, 2407.
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33. 13C NMR, 2D-COSY, NOESY, CH correlation, and GC/MS spectroscopy; see the Supporting Information
34. 2Et for 5 h at 78°C forms 11 (78%) and the cross Diels Alder cycloaddition product 16 (22%). (figure presented)
35. The insertion reaction of alkynes into Al-R (R= ethyl, isobutyl) or Al-H producing the corresponding Al-vinyl bond has been reported; see: Wilke, G. V.; Müller, H, Liebiegs Ann. Chem. 1960, 629, 222.
36. 3Al is unable to remove the methyde group (methyl with the pair of electrons) from the metal center.
37. Attempts to trap any organoaluminium complexes in situ by NMR spectroscopy were unsuccessful.
38. 5 No reaction was observed for terminal alkynes with functional electron-withdrawing groups.