Acyl nitroso Diels–Alder (ANDA) reaction of sorbate esters and sorbic alcohol derivatives

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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 (¹H–¹⁵N) criterion for ready distinction of regioisomers arising from such ANDA reactions.

1H–15N long-range HSQC NMR of natural 15N abundance 10e (aryl hydrogens

The acyl nitroso Diels–Alder (ANDA) reaction of sorbate derivatives: an X-ray and ¹⁵N NMR study with an application to amino-acid synthesis

Lee Bollans,^a   John Bacsa,^a   Jonathan A. Iggo,^a   Gareth A. Morris^b and   Andrew V. Stachulski*^a  

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^aRobert Robinson Laboratories, Department of Chemistry, University of Liverpool, Liverpool, UK
E-mail: stachuls@liv.ac.uk
Fax: 44 (0) 151 794 3588
Tel: 44 (0) 151 794 3542

^bSchool of Chemistry, University of Manchester, Oxford Rd., Manchester, UK

Org. Biomol. Chem., 2009,7, 4531-4538

http://pubs.rsc.org/en/content/articlelanding/2009/ob/b912963d#!divAbstract
DOI: 10.1039/B912963D                                                                                                                                                                                                                                                                                          ///////////