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Synlett 2008(18): 2874-2876  
DOI: 10.1055/s-0028-1083569
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of a Trihydroxylated Aminoazepane from d-Glucitol by an Intramolecular Aziridine Ring Opening

Marcelo Siqueira Valle, Raquel Marques Braga*
Instituto de Química, Universidade Estadual de Campinas, P.O. Box 6154, Campinas, SP 13084-971, Brazil
Fax: +55(19)35213023; e-Mail: raquel@iqm.unicamp.br;
Further Information

Publication History

Received 1 May 2008
Publication Date:
16 October 2008 (online)

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Abstract

Transformation of d-glucitol into its 1,6-diazido derivative allowed its conversion into the polyhydroxylated amino­azepane ring in a one-pot reaction using Ph3P and H2O.

Key words

azepanes - 1-deoxynojirimycin - iminosugars - aziridine

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9

Spectroscopic Data for (5 S )-Amino-(4 R )- O -benzyl-1,5,6-trideoxy-(2 S ,3 R )- O -isopropylidene-1,6-imino- d -glucitol (16, Figure 2)
R f = 0.2 (CHCl3-MeOH, 9:1; 2×). IR (KBr): 3360, 3291 (NH), 2851 (CH), 1070 (CN) cm-¹. MS: m/z (%) = 57 (16), 71 (21), 84 (26), 91 (100), 98 (49), 110 (8), 126 (34), 141 (7), 149 (10), 167 (14), 184 (27), 201 (23), 227 (3), 277 (10), 292 (2). ¹H NMR (500 MHz, CDCl3): δ = 1.43, 1.44 [6 H, 2 s, C(CH3)2], 2.13-2.18 (3 H, br s, NH aliphatic and cyclic), 2.71 (1 H, dd, ² J = 11.7 Hz, ³ J = 9.0 Hz, H1-α), 2.81 (1 H, dd, ² J = 14.4 Hz, ³ J = 6.8 Hz, H6-α), 2.89 (1 H, dd, ² J = 14.4 Hz, ³ J = 2.2 Hz, H6-β), 3.00 (1 H, ddd, ³ J = 6.8 Hz, ³ J = 4.6 Hz, ³ J = 2.2 Hz, H5), 3.37 (1 H, dd, ³ J = 9.0 Hz, ³ J = 4.6 Hz, H4), 3.40 (1 H, dd, ² J = 11.7 Hz, ³ J = 4.8 Hz, H1-β), 3.89 (1 H, td, ³ J = 9.0 Hz, ³ J = 4.8 Hz, H2), 4.01 (1 H, t, ³ J = 9.0 Hz, H3), 4.68 (1 H, d, ² J = 11.7 Hz, OCHH′C6H5), 4.93 (1 H, d, ² J = 11.7 Hz, OCHH′C6H5), 7.29 (1 H, t, ³ J = 7.4 Hz, H4′), 7.35 (2 H, t, ³ J = 7.4 Hz, H3′, H5′), 7.39 (2 H, d, ³ J = 7.4 Hz, H2′, H6′). ¹³C NMR (125 MHz, CDCl3): δ = 27.0, 27.2 [C(CH3)2], 49.2 (C6), 49.8 (C1), 55.9 (C5), 72.9 (OCH2C6H5), 75.9 (C2), 83.4 (C3), 85.8 (C4), 109.2 [C(CH3)2], 127.6 (C4′), 128.0 (C2′, C6′), 128.3 (C3′, C5′), 138.6 (C1′).