ON THE CATALYTIC AMIDOCARBONYLATION OF SUBSTITUTED ALLYLIC ALCOHOLS

Article abstract of DOI:10.1016/0022-328X(86)80089-4

Substituted allylic alcohols (3-methyl-2-buten-1-ol and 2-methyl-3-buten-2-ol) were isomerized and amidocarbonylated.In addition to the expected product, N-acetylleucine, arising from their rearrengement to 3-methylbutanal and subsequent amidocarbonylation (22percent yield), we isolated two additional products (28percent yield).These were shown by spectroscopic methods and by syntheses, via amidocarbonylations of the respective aldehydes, to be 2-acetamido-5-methylhexanoic acid and 2-acetamido-4-methylhexanoic acid.Their formation is postulated to be the sequential result of (i) dehydration first to form isoprene, (ii) hydroformylation and hydrogenation of isoprene to give 3-methyl-1-pentanal and 4-methyl-1-pentanal, and (iii) aldehyde amidocarbonylation.Treatment of isoprene itself under the same conditions also gave these latter two acetylamino acids.