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3Et-1a-c were prepared in higher yield (respectively 57%, 60%, and 51%) by treatment of 3Me-1a-c with LTMP (3 equiv, -50°C/THF) followed by trapping with iodomethane.
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Polyiodinated pyrazines formed by treatment of fluoropyrazine with LTMP followed by quench with elemental iodine were reported to arise from an halogen-dance involving a iodine-lithium exchange reaction and not from a polylithiated intermediate: Toudic, F.; Plé, N.; Turck, A.; Quéguiner, G. Tetrahedron 2002, 58, 283.
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2 and esterification affords a symmetrical 1,9-diester. The initially formed 1-carboxylate is able to direct a second deprotonation of the 9-position during the quench. The intermediacy of a Quadac is clearly dependent on the nature of the electrophile and the substrate to be metalated. See: Palmer, B. D.; Boyd, M.; Denny, W. A. J. Org. Chem. 1990, 55, 438. (Chemical Equation Presented)
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