| Abstract: | From a Base Catalyzed Ring Opening of 2H-Azirines to an α-Alkylation Method of Primary Amines It is shown that fluorene-9′-spiro-2-(3-phenyl-2H-azirine) ( 1 ) on treatment with various alcohols in the presence of the corresponding alkoxide ions yields N-(9′-fluorenyl)benzimidates 2a-d (Scheme 1). 2,2,3-Triphenyl-2H-azirine ( 3 ) reacts with methanol in a similar manner (Scheme 2). Benzimidates 2a (Scheme 3), 8 (Scheme 4) and and 10 (Scheme 5) can easily be deprotonated by butyllithium (BuLi) or lithium diisopropylamide (LDA) in tetrahydrofuran (THF) to 1-methoxy-2-aza-allylanions, that can be alkylated, at C(3), exclusively, by various electrophiles (e.g. R-X(X = I, Br), RCHO or methyl acrylate (see also Scheme 6)). As the acidic hydrolyses (1N HCl) of benzimidates 9 and 11 leads to the corresponding α-alkylated free amines 15 and 18 (Scheme 7 and 8), benzoyl derivatives 16 and 19 are obtained from the hydrolysis under basic conditions. On the other hand, it is observed that a catalyzed Chapman rearrangement of 9 and 11 results in the formation of N-benzoyl-N-methyl derivatives 17 and 20 (Scheme 7 and 8). The described reactions offer a simple method for the α-alkylation of activated primary amines. |
