The acyl nitroso Diels-Alder (ANDA) reaction of sorbate derivatives: an X-ray and 15N NMR study with an application to amino-acid synthesis.
We present a study of the acyl nitroso Diels-Alder (ANDA) reaction of sorbate esters and sorbic alcohol derivatives, using alkoxycarbonyl nitroso dienophiles. An optimisation of the reaction conditions for ethyl sorbate is first presented, and the product is used in an efficient synthesis of 5-methylornithine. Structure-reactivity trends in sorbic alcohol (E,E-2,4-hexadien-1-ol) and its acylated analogues are then discussed. We present single-crystal X-ray structural proof for key adducts in both series and present in detail a novel HMBC/HSQC ((1)H-(15)N) criterion for ready distinction of regioisomers arising from such ANDA reactions.
Bollans
Lee
L
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Liverpool, L69 7ZD, UK.
Bacsa
John
J
Iggo
Jonathan A
JA
Morris
Gareth A
GA
Stachulski
Andrew V
AV
D000438:Alcohols / Q000737:chemistry; D000596:Amino Acids / Q000138:chemical synthesis* / Q000737:chemistry; D018360:Crystallography, X-Ray; D004952:Esters / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009603:Nitroso Compounds / Q000737:chemistry*; D009952:Ornithine / Q000737:chemistry; D013011:Sorbic Acid / Q000031:analogs & derivatives* / Q000737:chemistry*; D013237:Stereoisomerism
D000438:Alcohols; D000596:Amino Acids; D004952:Esters; D009603:Nitroso Compounds; D009952:Ornithine; D013011:Sorbic Acid