Lewis Base-Catalyzed Allylic Alkylation ofα-Amino Nitriles and Cyanohydrins and Synthetic Applications

Abstract

This article summarized our recent progress in Lewis base-catalyzed the direct allylic substitutions of Morita-Baylis-Hillman (MBH) adducts with α-amino nitriles and cyanohydrins bearing an α-hydrogen, which provided efficient access to functionalized α-amino nitriles and cyanohydrins incorporating quaternary carbon centers. On the basis of these, a novel metal-free carbocyanation (alkenylcyanation and acylcyanation) approach to construct functionalized nitriles incorporating β-quaternary carbon center has been developed. In addition, the several factors influencing these chemical transformations are discussed, and the possible mechanism is proposed.

Direct C(sp3)–H allylation of 2-alkylpyridines with Morita–Baylis–Hillman carbonates via a tandem nucleophilic substitution/aza-Cope rearrangement

“…However, these reactions were mainly suitable to strong nucleophiles such as malonates, amines, or alcohols etc. [20][21][22][23]. The allylic substitution reactions using some weak nucleophiles, such as alkyl aza-arenes, were very limited [24][25][26][27][28][29].…”

Direct C(sp3)-H allylation of 2-alkylpyridines with Morita-Baylis-Hillman carbonates via a tandem nucleophilic substitution/aza-Cope rearrangement

“…These reactions typically proceed under the catalysis of nucleophilic tertiary amine or phosphine, and no metal catalysts are needed, which makes this strategy more synthetically useful for the construction of allyl-substituted scaffolds. However, these reactions were mainly suitable to strong nucleophiles such as malonates, amines, or alcohols etc [19][20][21].…”