Hetero Diels-Alder Reactions of 2-Chloro-1nitroso-1-phenylethene: Preparation of Novel 4-Chloro-Substituted 1,2-Oxazins and Subsequent Reactions

Reinhold Zimmer; Jörg Angermann; Ute Hain; Florian Hiller; Hans-Ulrich Reissig

doi:10.1055/s-1997-1373

Synthesis 1997; 1997(12): 1467-1474
DOI: 10.1055/s-1997-1373

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Hetero Diels-Alder Reactions of 2-Chloro-1nitroso-1-phenylethene: Preparation of Novel 4-Chloro-Substituted 1,2-Oxazins and Subsequent Reactions

Reinhold Zimmer, Jörg Angermann, Ute Hain, Florian Hiller, Hans-Ulrich Reissig^*

^*Institut für Organische Chemie der Technischen Universität Dresden, D-01062 Dresden, Germany, Fax +49(351)4637030; E-mail: hans.reissig@chemie.tu-dresden.de

Abstract

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The cycloaddition of 2-chloro-1-nitroso-1-phenylethene (3), generated in situ from 2,2-dichloro-1-phenylethan-1-one oxime (2) to electron-rich olefins, e.g. silyl enol ethers or alkyl enol ethers, furnished the 4-chloro-substituted 5,6-dihydro-4H-1,2-oxazines and 6H-1,2 oxazines in moderate to good yields and with good diastereoselectivities. Bromo enol ether 18 led to the unexpected α,α-dichloro oxime derivative 21 as well as the halogenated 6H-1,2-oxazines 19 and 20. Starting from 4-chloro-1,2-oxazines 5 and 17, 4-azido-, 4-amino-, 4-hydroxy-, and 4-oxo-substituted 1,2-oxazines were prepared. Hydrogenolysis of 5,6-dihydro-4H-1,2-oxazine 5 afforded amine 31.

1,2-oxazine - hetero Diels-Alder reaction - cis-dihydroxylation - hydrogenolysis - silyl enol ether

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