Isoprene-mediated lithiation of imidazole derivatives: Mechanistic considerations

Arkivoc

Volumn 2011, Issue 5, 2011, Pages 12-22

  Guijarro, Albert ^a   De La Viuda, Mónica ^a   Torregrosa, Rosario ^a   Peñafiel, Itziar ^a   Pastor, Isidro M ^a   Yus, Miguel ^a   Nájera, Carmen ^a  

^a UNIVERSITY OF ALICANTE   (Spain)

Author keywords

DFT calculations; Imidazole; Isoprene mediated lithiation; Lithium metal; Mechanism

Indexed keywords

EID: 79955386112     PISSN: 1551-7012     EISSN: 15517004     Source Type: Journal    
DOI: 10.3998/ark.5550190.0012.503     Document Type: Article

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51. 0K =-195.2505;?H° =-195.2443;?S° = 72.048;?G° =-195.2785.
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59. Unfortunately, those values are in the range of the absolute deviation (±0.21 eV) expected for this method according to the calculated EA data for 12 small molecules and compared with the corresponding experimental EA: Takahata, Y.; Chong, D. P. J. Braz. Chem. Soc 1999, 10, 354.
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61. 0K =-195.8350; ΔH ° =-195.8273; AS ° = 80.926; AG° =-195.8658
62. 0K =-246.8852; ΔH ° =-264.8789; AS ° = 73.473; AG° =-264.9138.
63. 0K =-272.4456; AH° =-272.4383; AS° = 73.473; AG° =-272.4756.
64. 0K =-203.3896; Æ° =-203.3813; AS ° = 80.498; AG° =-203.4195
65. The electron affinity of 8· is EA = +0.37 eV.
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67. 0K =-196.4658; Æ° =-196.4579; AS ° = 79.501; AG° =-196.4957.
68. After performing the reaction employing the standard conditions (excess of lithium, 20 mol% of isoprene in THF at 25 °C), the presence of 2-methyl-2-butene was detected in the reaction medium by GC-MS (EI at 70 eV on an Agilent 5973 spectrometer).