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PO
PO
OP
OP
12b: P = Piv, E/Z 87:13
12c: P = MOM, E/Z 89:11
13b: P = Piv, 60:40
13c: P = MOM, 64:36
c
CBz
CBz
CN
CN
N
N
+
MOMO
OMOM
MOMO
OMOM
14c
15c
d
d
CBz
N
CBz
N
CN
OMOM
OMOM
CN
OMOM
OMOM
16c
17c
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Scheme 3. Synthesis of unsaturated azepanes 16c and 17c. Reagents and condi-
tions: (a) (EtO)2PO-CH2-CN (1 equiv), Et3N (2.1 equiv), LiCl (4 equiv), rt, 5 h, 90% for
12b, 68% for 12c; (b) allylamine (4 equiv), methanol, 35 °C, 3 days, 54% for 13b, 76%
for 13c; (c) CBz-Cl (2.1 equiv), NaHCO3 (19 equiv), EtOAc/H2O 1:1, 0 °C 1 h then rt
12 h, 72% (mixture of diastereomers) for 14c–15c; (d) Grubbs’s I catalyst (15 mol %),
toluene, 90 °C, 3 days, 80% for 16c, 60% for 17c.
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Tetrahedron 2010, 66, 4109–4114.
17. For
a review, see: Compain, P.; Chagnault, V.; Martin, O. R. Tetrahedron:
Asymmetry 2009, 20, 672–711.
(cyano)methyl groups at the pseudo-anomeric position, starting
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phosphonate group at the pseudo-anomeric position to prepare
compounds designed as potential inhibitors of glycosyltransferases
or glycogen phosphorylase will be undertaken. Further transforma-
tions of the double bond by a syn- or anti-dihydroxylation or amin-
ohydroxylation as well as modification of ester or nitrile group are
currently underway to afford a new series of polyhydroxylated
azepanes, with the aim of assessing their activities on commer-
cially available glycosidases.
Acknowledgements
This work was supported by the ‘Contrat de Plan Etat-Région’
(GLYCOVAL, PentoRaf, and PlAneT programs). The authors are
grateful to the ‘Ministère de l’Enseignement Supérieur et de la
Recherche’ and FEDER for financial support and a doctoral fellow-
ship (H.T.) and to the ‘Fondation du Site Paris-Reims’ for a post-
doctoral fellowship (S.G.). The authors also warmly thank Dr. D.
Harakat and Ms. A. Martinez for ESI-MS and NMR spectra recording
and for helpful discussions.
23. Davies, S. G.; Hughes, D. G.; Price, P. D.; Roberts, P. M.; Russell, A. J.; Thomson, J.
E.; Williams, O. M. J. Synlett 2010, 567–570.
24. Brock, E. A.; Davies, S. G.; Lee, J. A.; Roberts, P. M.; Thomson, J. E. Org. Lett. 2011,
13, 1594–1597.
25. General procedure for the conjugated addition of allylamine. Preparation of (4S, 5S)
ethyl 3-allylamino-N-benzyloxycarbonyl-4,5-bis(pivaloyloxy)hept-6-enoate (8b–
9b). A solution of allylamine (4 mL, 48 mmol, 12 equiv) and unsaturated ester
6b (1.6 g, 4 mmol) was stirred at room temperature for 72 h under argon. The
reaction was then concentrated in vacuo and the crude mixture was diluted in
diethyl ether (20 mL) and washed with 1 M HCl (20 mL) and brine (20 mL). The
organic phase was dried over anhydrous Na2SO4, filtrated, and concentrated to
dryness. The mixture of diastereomers was purified by flash chromatography
over silica gel (petroleum ether/diethyl ether 85:15) to afford 7b as a yellow oil
(1.1 g, 66%).
References and notes
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Pure compound 7b (mixture of diastereomers) (1.0 g, 2.5 mmol) was dissolved
in EtOAc/water 1:1 mixture (40 mL) and sodium hydrogenocarbonate (3.95 g,
47.5 mmol, 19 equiv) was added. Benzyl chloroformate (0.74 mL, 5.25 mmol,
2.1 equiv) was then added dropwise and the reaction mixture was kept at
room temperature for 12 h. The crude mixture was diluted in EtOAc (50 mL),
washed with 1 M HCl (2 ꢀ 50 mL) and brine (2 ꢀ 50 mL). The organic phase
was dried over anhydrous Na2SO4, filtrated, and concentrated to dryness. The
mixture of diastereomers was purified by flash chromatography over silica gel
(petroleum ether/diethyl ether 85:15) to afford pure 8b (0.66 g, 50%) and pure
9b (0.54 g, 40%) as yellow oils.
6. (a) Stütz, A. E., Ed. Iminosugars as Glycosidase Inhibitors: Nojirimycin and
Beyond; Wiley-VCH: Weinheim, Germany, 1999; (b) Pearson, M. S. M.; Mathé-
(3S, 4S, 5S) Ethyl 3-allylamino-N-benzyloxycarbonyl-4,5-bis(pivaloyloxy)hept-6-
enoate (8b). 1:1 Mixture of rotamers; ½a D19
= ꢂ16 (c 0.82, CHCl3); IR (film) mmax
ꢁ