Nucleophilic tert-butyllithium

Notice that tert-butyl radicals add readily to electrophilic alkenes using tert-butyl Grignards or tert-butyllithium as nucleophiles is much more problematic. 

In one series of experiments the a-lithiated silanes were produced by a nucleophilic addition of tert-butyllithium to the C=C double bond of a vinylhalosilane so that the 1,2-elimination led to a silene carrying a neopentyl substituent on the unsaturated carbon... 

The ring strain of norbomene is moderate, comparable with that of cyclobutene. tert-Butyllithium adds nucleophilically onto norbomene in ligroin or triethylamine but not in diethyl ether. 

Self-condensations are another set of important reactions of organolithium compounds. Tamao and Kawachi had reported that [(tert-butoxy diphenyl)silyl]lithium (20) exhibited ambiphUic character, and underwent a self-condensation reaction to give a [2- tert-butoxy)disilynyl]lithium derivative in THF as shown in Scheme 4, and also a nucleophilic substitution reaction with n-butyllithium . 

Treatment of 1,2,4-triazine 22 with organolithium compounds results in the formation of adducts 23 (yields 8-18%), whereas the reaction of 22 with tert- mX - or -butyllithium as C-nucleophiles affords the hexahydrotriazine 24 (Scheme 15) <2002J(P1)2549>. 

Their carbonyl function being flanked by two organic groups, ketones are less reactive toward nucleophiles than are aldehydes. Nevertheless even di-tert-butyl ketone combines with /erf-butyllithium in apolar media.Lithium tris-te/ /-butylcarbinolate is formed in excellent yield (81%) and proves perfectly stable. Contrarily, the addition of... 

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