Di- and trisubstituted γ-lactams via Rh(II)-carbenoid reaction of N-Cα-branched, N-bis(trimethylsilyl)methyl α-diazoamides. Synthesis of (±)-α-allokainic acid.
Acyclic N-C(α)-branched, N-bis(trimethylsilyl)methyl (N-BTMSM) diazoamides undergo regio-, chemo-, and diastereoselective Rh(II)-carbenoid C-H insertion to give 4,5-disubstituted and 3,4,5-trisubstituted γ-lactams. The conformational influence of the N-BTMSM group and the electronic effect of the O-pivaloyl moiety of the C(α)-oxymethylene unit are essential for the observed regioselectivity. The synthesis of α-allokainic acid demonstrates the utility of the method.
Department of Chemistry and Biochemistry, University of Regina, Regina, Saskatchewan, Canada S4S 0A2.
Bao
B
Zhang
Andrew G H
AG
Wee
D000577:Amides / Q000737:chemistry*; D001391:Azo Compounds / Q000737:chemistry*; D007608:Kainic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D007769:Lactams / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*; D014297:Trimethylsilyl Compounds / Q000737:chemistry*
D000577:Amides; D001391:Azo Compounds; D007769:Lactams; D014297:Trimethylsilyl Compounds; C495695:allokainic acid; C030011:carbene; D012238:Rhodium; D008697:Methane; D007608:Kainic Acid