Synthetic Approach to N-Alkylated 2,5-Diamino-2,5-dideoxy-1,4;3,6- dianhydroalditols by Reductive Alkylation

Gerrit Limberg; Joachim Thiem

doi:10.1055/s-1994-25468

Synthesis 1994; 1994(3): 317-321
DOI: 10.1055/s-1994-25468

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Synthetic Approach to N-Alkylated 2,5-Diamino-2,5-dideoxy-1,4;3,6- dianhydroalditols by Reductive Alkylation

Gerrit Limberg^* , Joachim Thiem

^*Institut für Organische Chemie, Universität Hamburg, Martin-Luther-King-Platz 6, D-20146 Hamburg, Germany

Abstract

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N,N′-Dialkylated 2,5-diamnno-2,5-dideoxy-1,4;3, 6-dianhydroalditols, representing interesting basic catalysts for polyaddition reactions, are synthesized by different reductive alkylation procedures in satisfactory yields. D-Gluco- and L-ido-N, N′-dialkyl-2,5-diamino-2,5-dideoxy-1,4;3,6-dianhydroalditols 7-8, 10-15 are accessible by reaction of the corresponding diamines with carbonyl compounds and reduction of the intermediately formed imine. For the synthesis of D-manno-N,N′-dialkylated diamines, an alternative route via 1,4;3,6-dianhydro-D-threo-2,5-hexodiulose (18) is established, thus avoiding the six-step synthesis towards 1,4;3,6-dianhydro-D-mannitol (2). Reductive alkylation of diketone 18 yields stereospecifically only the alkylated diamine 21 with D-manno-configuration. In case of the monoketones only 1,4;3,6-dianhydro-L-sorbose (16) can be transformed stereospecifically to N-2-pentyl-5-amino-5-deoxy-1,4;3,6-dianhydro-D-sorbitol (19), whereas 1,4;3,6-dianhydro-D-fructose (17) yields a mixture of D-manno- and D-gluco-monoamines 20a and 20b by reductive alkylation with 2-pentylamine and sodium borohydride.

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