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Acid‐Induced and Reductive Transformations of Enantiopure 3,6‐Dihydro‐2 H ‐1,2‐oxazines – Synthesis of Dideoxyamino Carbohydrate Derivatives
Author(s) -
Bressel Bettina,
Egart Boris,
AlHarrasi Ahmed,
Pulz Robert,
Reißig HansUlrich,
Brüdgam Irene
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700792
Subject(s) - oxazines , enantiopure drug , chemistry , pyran , solvolysis , bond cleavage , organic chemistry , medicinal chemistry , stereochemistry , combinatorial chemistry , catalysis , hydrolysis , enantioselective synthesis
Acid‐catalyzed transformations of carbohydrate‐derived 3,6‐dihydro‐2 H ‐1,2‐oxazines such as 1 , 5 and 13 provided a set of enantiopure furano‐1,2‐oxazines or pyrano‐1,2‐oxazines. The reaction conditions determined the degree of solvolysis of the compounds. An X‐ray analysis of product 6 revealed an interesting network of hydrogen bonds. Reductive cleavage of the N–O bond of the 1,2‐oxazines either by hydrogen/palladium or by samarium diiodide furnished enantiopure aminofuran and ‐pyran derivatives, e.g. 9 and 11 or compound 16 , which can be regarded as protected 4‐amino‐1,4‐dideoxyhex‐3‐ulose or 4‐amino‐1,4‐dideoxyoct‐3‐ulose derivatives. We thus have established a short and stereocontrolled route to amino carbohydrate derivatives with 1,2‐oxazines as crucial relay compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)