Hydride-transfer domino rearrangement of glycine-containing dioxa-azawurtzitane.
The novel synthetic method for dioxa-azawurtzitanes to selectively cap amino groups in amino acids or peptides is described. Mixing the CH(3)CN solution of cis,cis-1,3,5-triformyl-1,3,5-trimethylcyclohexane (2) with the aqueous solution of the equimolar amounts of glycine and NaHCO(3) yields glycine-containing dioxa-azawurtzitane 7-Na. Dioxa-azawurtzitane 7-Na almost quantitatively isomerizes to lactone-imine 9-Na through the hydride-transfer rearrangement in CH(3)CN/H(2)O. Lactone-imine 9-Na also isomerizes to lactam-aldehyde 12-Na in DMSO.
Izumi
Hiroshi
H
National Institute of Advanced Industrial Science and Technology, AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan. izumi.h@aist.go.jp
Futamura
Shigeru
S
D000596:Amino Acids / Q000737:chemistry; D001372:Aza Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods; D003510:Cyclohexanes / Q000138:chemical synthesis* / Q000737:chemistry; D004146:Dioxanes / Q000138:chemical synthesis / Q000737:chemistry; D005998:Glycine / Q000031:analogs & derivatives / Q000138:chemical synthesis / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D007783:Lactones / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010455:Peptides / Q000737:chemistry; D013237:Stereoisomerism; D014233:Tricarboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry
C452447:1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid; D000596:Amino Acids; D001372:Aza Compounds; D001952:Bridged-Ring Compounds; D003510:Cyclohexanes; D004146:Dioxanes; D007097:Imines; D007783:Lactones; D010455:Peptides; D014233:Tricarboxylic Acids; D006859:Hydrogen; D005998:Glycine