Palladium-catalyzed [3,3]-rearrangement for the facile synthesis of allenamides.
A [3,3]-rearrangement that is used for facile construction of chiral allenamides is described. A propargylic alcohol, a chlorophosphite, and Cbz-azide are combined to provide a propargylic phosphorimidate that, in the presence of catalytic palladium(II), rearranges to an allenamide. By varying the substitution pattern on the propargylic alcohol, mono-, di-, and trisubstituted allenamides can be accessed in good yields. Additionally, the use of an enantiomerically enriched propargylic alcohol enables the preparation of stereochemically defined allenamides.
Danowitz
Amy M
AM
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.
Taylor
Christopher E
CE
Shrikian
Tamar M
TM
Mapp
Anna K
AK
D000480:Alkynes / Q000737:chemistry; D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D020650:Combinatorial Chemistry Techniques; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D017905:Phosphites / Q000737:chemistry; D020005:Propanols / Q000737:chemistry; D013237:Stereoisomerism
D000480:Alkynes; D000577:Amides; D017905:Phosphites; D020005:Propanols; D010165:Palladium; C028255:propargyl alcohol