Kulinkovich-de-Meijere reaction

The other significant variation of the prototypical Kulinkovich reaction is the so-called Kulinkovich-de Meijere reaction, where de Meijere extended the substrates from esters to amides. Other carboxylic acid derivatives including (cyclic) carbonate, imides, and nitriles also react with the key Kulinkovich intermediate. Szymoniak developed an efficient new synthesis of cyclopropanes via hydrozirconation of allylic ethers (e.g., using Cp2Zr(H)Cl) followed by addition of a Lewis acid (e.g., BFa OEta). Casey et al. further investigated the stereochemistry of this interesting cyclopropanation reaction using deuterated allylic ethers. ... 

Joullie took advantage of the Kulinkovich-de Meijere reaction and synthesized a series of constrained A, A -dialkyl neurotransmitter analogues. For instance, indolylcyclopropylamine 50 was assembled from indole-olefm 49 and DMF in 52% yield. 

While intermolecular Kulinkovich-de Meijere reaction assembles cyclopropylamine, many have taken advantage of a pendent olefin at the substrates to synthesize bicycles. Cha converted olefinyl amide 51 to bicyclic amine 52 in excellent yields. Six and co-workers prepared eight bicyclic aminocyclopropanes including 54 (from substrate 53) with yields ranging from 26 to 87%. ... 

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