Microwave-Induced, InCl₃-CatalyzedFerrier Rearrangement of Acetyl­glycals: Synthesis of 2,3-UnsaturatedGlycopyranosides [1]

Abstract

Indium(III) chloride catalyzed, microwave assisted Ferrier rearrangementon different per-O-acetylglycals leadsto an efficient synthesis of 2,3-unsaturated O-glycosidesin good to excellent yields.

Key words

indium(III) chloride - microwave - Ferrierrearrangement - glycals - O-glycosides

1

DRL Publication No. 321.

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1

DRL Publication No. 321.

16

A Typical Procedure:To a solution of glycal (50 mg) and alcohol (2 equiv) in acetonitrile(1 mL) InCl₃ (30 mol%) was added and the mixtureirradiated with microwaves (LG model: MC-804AAR) for the appropriatetime (see Table [1] ). Thereaction mixture was then diluted with ethyl acetate and washedwith water, dried (Na₂SO₄) and evaporatedto dryness. The residue was purified on silica gel (100-200 mesh)to afford the desired 2,3-unsaturated products as summarized inTable [1] .

18

All new compounds were fully characterized.Spectral and analytical data were in good agreement. Spectral dataof (2 S ,3 R ,6 R )-2-methyl-6-phenethyloxy-3,6-dihydro-2 H -3-pyranyl acetate: ¹HNMR (CDCl₃, 400 MHz): δ 1.16 (d, 3 H, J = 6.4 Hz, H-6), 2.08 (s, 3H, Ac), 2.93 (t, 2 H, J = 7.1 Hz,PhCH ₂), 3.76 (t, 1 H, J = 7.1 Hz, OCH₂),3.83-3.90 (m, 1 H, H-5), 3.98 (t, 1 H, J = 7.1Hz, OCH₂), 4.95 (br s, 1H, H-1), 5.03 (dd, 1 H, J = 9.3 Hz, 1.5 Hz, H-4), 5.77(dd, 1 H, J = 10.3Hz, 1.9 Hz, H-2), 5.84 (dd, 1 H, J = 10.3Hz, 1.9 Hz, H-3), 7.20-7.32 (m, 5 H, Ph). IR (Neat): 1745,1374, 1237, 1107, 1039, 918 cm^-1. LC-MS(CI): m/z 277 (M⁺ + 1).
(6 S ,2 R ,3 R )-2-Methylcarbonyloxymethyl-6-(2-propyn-yloxy)-3,6-dihydro-2 H -3-pyranyl acetate: ¹HNMR (CDCl₃, 400 MHz): δ 2.076, 2.084 (2 s, 6H, 2Ac), 2.93 (t, 1 H, J = 2.4Hz, acetylene H), 4.22-4.32 (m, 5 H, H-5, H-6, OCH₂),5.04 (dd, 1 H, J = 5.4 Hz, 2.4Hz, H-4), 5.29 (d, 1 H, J = 2.9Hz, H-1), 6.04 (dd, 1 H, J = 10.3Hz, 2.9 Hz, H-2), 6.15 (ddd, 1 H, J = 10.0Hz, 5.4 Hz, 1.0 Hz, H-3). IR (Neat): 1743, 1590, 1372, 1234, 1102,1039, 757 cm^-1.
LC-MS (CI): m/z 269 (M⁺ + 1).
(6 S ,2 R ,3 R )-2-Methylcarbonyloxymethyl-6-(4-pentenyl-oxy)-3,6-dihydro-2 H -3-pyranyl acetate: ¹HNMR (CDCl₃, 400 MHz): δ 2.08, 2.09 (2 s, 6 H,2Ac), 1.66-1.78 (m, 2 H, OCH₂CH ₂CH₂-),2.10-2.20 (m, 2 H, OCH₂CH₂CH ₂-), 3.50-3.59 (m,1 H, OCH ₂CH₂CH₂-),3.75-3.84 (m, 1 H, OCH ₂CH₂CH₂-),4.20-4.09 (m, 2 H, H-6), 4.33-4.40 (m, 1 H, H-5),4.95-5.04 (m, 3 H, H-4 and CH=CH ₂),5.06 (d, 1 H, J = 2.0 Hz, H-1),5.77-5.87 (m, 1 H, CH=CH₂)_, 6.03(dd, 1 H, J = 10.2 Hz, 2.9 Hz,H-2), 6.15 (ddd, 1 H, J = 10.0Hz, 5.4 Hz, 1.0 Hz, H-3). IR (Neat): 1744, 1372, 1232, 1106, 1049, 912cm^-1. LC-MS (CI): m/z 299(M⁺ + 1).
(3 R ,6 R )-3-Allyloxy-3,6-dihydro-2 H -3-pyranyl acetate (majorisomer): ¹H NMR (CDCl₃, 400MHz): δ 2.09 (s, 3 H, Ac), 3.80-3.87 (m, 1 H,OCH ₂CH=CH₂),4.07 (dd, 1 H, J = 7.8Hz, 1.5 Hz, H-5a), 4.09-4.20 (m, 1 H, OCH ₂CH=CH₂),4.24 (dd, 1 H, J = 6.4 Hz, 1.5Hz, H-5b), 4.94-4.97 (m, 1 H, H-4), 5.05 (d, 1 H, J = 2.4 Hz, H-1), 5.18-5.33(m, 2 H, OCH₂CH=CH ₂),5.83-5.98 (m, 1 H, OCH₂CH=CH₂),6.04 (dd, 1 H, J = 10.0 Hz,3.0 Hz, H-2), 6.09 (dd, 1 H, J = 10.2Hz, 4.9 Hz, H-3). IR (Neat): 1738, 1373, 1238, 1102, 1042, 959 cm^-1.LC-MS (CI): m/z 199 (M⁺ + 1).