Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1) → tert-Butyl 2-(2-(1-(3-hydroxyphenyl)-2-oxabicyclo[2.2.2]octan-4-yl)ethoxy)acetate

HRID 1855046Notes

Reaction equation

O1CCCCC1[O:7][C:8]1[CH:9]=[C:10]([C:14]23[CH2:21][CH2:20][C:17]([CH2:22][CH2:23][O:24][CH2:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([CH2:18][CH2:19]2)[CH2:16][O:15]3)[CH:11]=[CH:12][CH:13]=1.CC1C=CC(S([O-])(=O)=O)=CC=1.C1C=C[NH+]=CC=1>CO>[OH:7][C:8]1[CH:9]=[C:10]([C:14]23[CH2:19][CH2:18][C:17]([CH2:22][CH2:23][O:24][CH2:25][C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([CH2:20][CH2:21]2)[CH2:16][O:15]3)[CH:11]=[CH:12][CH:13]=1

Participants

Conditions

Temperature: 50 °C

Procedure

A mixture of tert-butyl 2-(2-(1-(3-(tetrahydro-2H-pyran-2-yloxy)phenyl)-2-oxabicyclo[2.2.2]octan-4-yl)ethoxy)acetate (1000 mg, 2.24 mmol) and PPTS (169 mg, 0.672 mmol) in MeOH (10 ml) was stirred at 50° C. for 3 h. The reaction was concentrated in vacuo. The crude oil was purified by flash chromatography on SiO2 (0 to 30% EtOAc:hexanes) to afford the title compound (723 mg, 89% yield) as a white solid. LCMS, [M−H]+=361.4. 1H NMR (500 MHz, CDCl3) δ 7.19 (t, J=8.1 Hz, 1H), 6.96-6.91 (m, 2H), 6.71 (ddd, J=8.0, 2.5, 1.0 Hz, 1H), 4.83 (s, 1H), 3.96 (s, 2H), 3.89 (s, 2H), 3.59 (t, J=6.9 Hz, 2H), 2.06-2.00 (m, 4H), 1.78-1.71 (m, 4H), 1.54 (t, J=7.0 Hz, 2H), 1.51 (s, 9H).

Workup

concentrationThe reaction was concentrated in vacuo
customThe crude oil was purified by flash chromatography on SiO2 (0 to 30% EtOAc:hexanes)

Sources & evidence

ORD record: ord-af457f4f98bf411a9f5a512acfd4f017
Source dataset: uspto-grants-2015_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08962660B2

Reaction notes

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