Imidates including cyclic imidates

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

“…As mentioned above, the aryl N-benzimidates have the capacity to rearrange via an 1,3-aryl shift (Chapman rearrangement) and transform into amides. [2,3] Recently, a Ni-catalyzed rearrangement was developed for the transformation of N-benzyl imidates 211 to the desired products 212 via a [1,4]-aryl migration. [88] This method combined Ni(cod) 2 as the most appropriate catalyst and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) as the ligand, at 160 °C.…”

“…[2,3] Based on the geometry of the C=N double bond and the substituents' priority, acyclic imidates can have E or Z configuration (Figure 2). According to the most recent chapter by Neilson in The Chemistry of Amidines and Imidates, [4] when the substituents R and R' are alkyl groups, these compounds occur mainly in the E configuration, with the Z isomers being thermodynamically unstable. The same is observed when the R substituent is an aromatic group.…”

“…The most recent review of the known syntheses of imidates was written by Neilson in 1991 in the book “The Chemistry of Amidines and Imidates” , [4] as a continuation of the author‘s previous work, [5] where different synthetic routes, based on the variety of the types of starting materials, were classified. Thus, resulting categories were the use of nitriles and alcohols under acidic (Pinner reaction) or basic conditions, reactions of imidoyl halides with alcohols and phenoxides, conversion of amides to imidates, reactions of amino compounds with ortho‐esters, transesterification of imidates, synthesis of N ‐substituted imidates from unsubstituted imidates, synthesis from unsaturated systems or from metal complexes and organometallic compounds.…”