Ring Enlargement of Carbohydrate-Derived 1,2-Oxazines to Enantiopure 5-Bromo-1,2-oxazepines and Subsequent Palladium-Catalyzed Reactions

A. Al-Harrasi, S. Fischer, R. Zimmer, H.-U. Reissig – 2010

Dibromocarbene addition to d-glyceraldehyde-derived 1,2-oxazines syn -1 and anti -1 provided dibromocyclopropane intermediates syn-3 and anti-3, which smoothly reacted with methanol under ring enlargement to furnish 5-bromo-1,2-oxazepine derivatives syn -4 and anti -4. Related 1,2-oxazines such as arabinose-derived­ compounds furnished the 1,2-oxazepine derivatives syn-4e and anti-4f with fair efficacy. The alkenyl bromide moiety of 1,2-oxazepine derivatives syn -4 and anti -4 was then exploited for the introduction of new substituents via palladium-catalyzed C-C bond forming processes (Sonogashira, Suzuki, Stille, and Heck reactions). These transformations led to a series of new highly substituted 1,2-oxazepine derivatives syn-5 or anti-5-11 being of considerable interest for further synthetic elaborations.

Titel
Ring Enlargement of Carbohydrate-Derived 1,2-Oxazines to Enantiopure 5-Bromo-1,2-oxazepines and Subsequent Palladium-Catalyzed Reactions
Verfasser
A. Al-Harrasi, S. Fischer, R. Zimmer, H.-U. Reissig
Datum
2010
Kennung
10.1055/s-0029-1217126
Zitierweise
Synthesis 2010, 304-314
Art
Text
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