(3AR,5R)-5-((benzyloxy)methyl)-3a,4,5,7-tetrahydro-3H-pyrano[3,4-c]isoxazole → 2-{[(1R,3E)-1-cyclopropylpent-3-en-1-yl]oxy}-N-hydroxyethanimine

HRID 1478720Notes

Reaction equation

HRID 1478720 reaction equation
C(O[CH:4](OCC)[CH2:5][O:6][C@@H:7]([CH:12]1[CH2:14][CH2:13]1)[CH2:8]/[CH:9]=[CH:10]/[CH3:11])C.C(OC[C@H](OCC=[N:34][OH:35])CC=C)C1C=CC=CC=1.C(OC(OCC)CO[C@H](CC=C)COCC1C=CC=CC=1)C.C(OC[C@@H]1OCC2=NOC[C@@H]2C1)C1C=CC=CC=1>>[CH:12]1([C@H:7]([O:6][CH2:5][CH:4]=[N:34][OH:35])[CH2:8]/[CH:9]=[CH:10]/[CH3:11])[CH2:14][CH2:13]1

Participants

5

Reactant 4

HCID 57475687(3AR,5R)-5-((benzyloxy)methyl)-3a,4,5,7-tetrahydro-3H-pyrano[3,4-c]isoxazoleHCID 59281174[(R)-2-(2,2-diethoxyethoxy)-4-pentenyloxymethyl]benzeneHCID 86640913((R)-1-benzyloxymethyl-3-butenyloxy)acetaldehyde oximeHCID 90253549HCID 90253549, compound

Product 1

HCID 1317365212-{[(1R,3E)-1-cyclopropylpent-3-en-1-yl]oxy}-N-hydroxyethanimine

Procedure

[(1R,3E)-1-(2,2-Diethoxyethoxyl)pent-3-en-1-yl]cyclopropane (C25) was converted to the product using the method described for synthesis of 2-{[(2R)-1-(benzyloxy)pent-4-en-2-yl]oxy}-N-hydroxyethanimine (C3) in the section “Alternate conversion of C2 to C4.” In this case, purification was carried out using silica gel chromatography (Gradient: 0% to 80% ethyl acetate in heptane) to provide the product as a colorless oil. By 1H NMR, this was assigned as a roughly 1:1 mixture of oxime isomers. Yield: 200 mg, 1.09 mmol, 48%. 1H NMR (400 MHz, CDCl3), characteristic peaks: δ [7.50 (dd, J=5.8, 5.6 Hz) and 6.93 (dd, J=3.6, 3.6 Hz), total 1H], 7.46 and 7.21 (2 br s, total 1H), 5.45-5.63 (m, 2H), {[4.50 (dd, half of ABX pattern, J=16.3, 3.6 Hz) and 4.40 (dd, half of ABX pattern, J=16.3, 3.7 Hz)] and [4.25 (dd, half of ABX pattern, J=12.8, 5.6 Hz) and 4.15 (dd, half of ABX pattern, J=12.9, 5.8 Hz)], total 2H}, 2.59-2.68 (m, 1H), 1.66-1.72 (m, 3H), 0.45-0.54 (m, 1H), 0.29-0.43 (m, 1H), 0.18-0.24 and 0.06-0.14 (2 m, total 1H).

Workup

  1. custom” In this case, purification

Sources & evidence

ORD record
ord-224c4b183f074d739a93741a4b8ef59d
Source dataset
uspto-grants-2016_08
Patent number
US09403846B2

Reaction notes

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