Unsaturated hydroxylactams

Nickel-catalyzed carbonylation of a-ketoalkynes has also been reported by Arzoumanian et al. under phase-transfer conditions.94 The carbonylation gave either furanone or unsaturated carboxylic acids depending on the substituents of substrates (Eq. 4.53). A similar reaction, nickel-catalyzed cyanation of a-ketoalkynes with KCN in water, was also reported to afford unsaturated hydroxylactams (Eq. 4.54).95... 

This process was also extended to the formation of /3-hydroxylactams from a ,/3-unsaturated amides with tethered keto-amides 249 (Scheme 111) (179-181). Various substrates underwent cyclizations resulting in the corresponding /3-hydroxylactams 250 with high diastereoselectivities (>95 5) and moderate yields (52-70%). The reaction was tolerant of a wide range of ketones including alkyl, aromatic, and heteroaromatic ketones. Substituents on the /3-position of a,p-unsaturated amides were not well tolerated. Acryloyl amides were found to be the best substrates for this type of cyclization. In addition, crotonoyl amide also underwent cyclization, but conversions and reaction rates were diminished. A... 

---