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Volumn 55, Issue 1, 1999, Pages 29-62

Synthesis and cycloaromatization kinetics of aromatic allene enynes

Author keywords

[No Author keywords available]

Indexed keywords

ALLENE DERIVATIVE;

EID: 0032900736     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)01022-9     Document Type: Article
Times cited : (27)

References (91)
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    • note
    • It is possible that the decomposition process is an intramolecular cycloaromatization of the allenic phosphorane (shown below), which would account for the extreme sensitivity of the synthetic methodology to the size of the alkyne substituent, in analogy to the all-carbon analogue described in the text. (equation presented)
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    • note
    • Geometry minimization was performed using the MM2 force field as implemented in Macromodel versions 4.0 and 4.5. For each compound, a Monte Carlo conformational search of enough starting structures (usually 1000) to generate ten or more duplicates of the first ten energy minima was performed.
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    • note
    • The same molecular mechanics analysis of the Saito compound 6 (R=H) shows the s-trans conformation to be the more stable, but the calculated energy difference is much smaller (0.25 kcal/mol) than reported for the ab intio method.
  • 66
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    • note
    • At 25°C, the difference in ΔH‡ (-1.7 kcal/mol) alone would lead to an 18-fold rate acceleration for 2b, and the difference in ΔS‡ provides a 14-fold rate enhancement in the same direction.
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    • note
    • We also observed no kinetic resolution of racemic allenes such as 4a in cycloaromatization reactions conducted in enantiomerically pure chiral alcohol solvents (α-phenethyl alcohol, 2-butanol), even at high conversions.
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    • Experimental measurements and calculations by Squires and coworkers have established that the parent α,3-dehydrotoluene diradical has a spin-coupled (singlet) ground state: Wenthold, P.G.; Wierschke, S.G.; Nash, J.J.; Squires, R.R. J. Am. Chem. Soc. 1993, 115, 12611-12612; Wenthold, P.G.; Wierschke,S.G.; Nash, J.J.; Squires, R.R. J. Am. Chem. Soc. 1994, 116, 7378-7392.
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    • Experimental measurements and calculations by Squires and coworkers have established that the parentα,3-dehydrotoluene diradical has a spin-coupled (singlet) ground state: Wenthold, P.G.; Wierschke,S.G.; Nash, J.J.; Squires, R.R. J. Am. Chem. Soc. 1993, 115, 12611-12612; Wenthold, P.G.; Wierschke, S.G.; Nash, J.J.; Squires, R.R. J. Am. Chem. Soc. 1994, 116, 7378-7392.
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    • In this context, it is interesting to note the rate difference between aromatic allene-ynes 4g and 31: at 37°C, the reported half life of 31 (23 h) (Nicolaou, K.C.; Maligres, P.; Shin, J.; de Leon, E.; Rideout, D. J. Am. Chem. Soc. 1990, 112, 7825-7826) is approximately 14 times that of 4g at 37.7 °C in 1,4-cyclohexadiene (Table 6, entry 20). Thus, the phosphoryl residue of 31 proves to be severely destabilizing to the transition state relative to the p-tolyl group of 4g. (equation presented)
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