Nitrenoids LiRN–OR1 in electrophilic amination reactions of organolithium compounds. A theoretical study

Abstract

The lithium alkoxyamides LiRN–OR¹(2), in contrast to the alkoxyamines HRN–OR¹(1), react with the organolithium compounds R²–Li to provide the amines HRN–R²(on hydrolysis); M.O. calculations indicate that the facile substitution of R¹O^– in (2) is due to (i) the formation of a LiRN–OR¹·LiR² dimer, (ii) a long N–O bond in (2), and (iii) the high stability of LiNH⁺.