Dimethyl Sulfide → HCID 86701329, compound

HRID 2283020Notes

Reaction equation

HRID 2283020 reaction equation
[CH2:1]([O:4][C@H:5]1[C@H:13]([CH3:14])[O:12][C:11](=[O:15])[C@@H:10]([N:16]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH2:9][O:8][CH2:7][C@@H:6]1[O:31][CH2:32][CH2:33][CH2:34][CH3:35])[CH:2]=C.C([O-])(O)=[O:37].[Na+].O=[O+][O-].CSC>CO.C(Cl)Cl>[C:19]([O:18][C:17]([N:16]([C@H:10]1[CH2:9][O:8][CH2:7][C@H:6]([O:31][CH2:32][CH2:33][CH2:34][CH3:35])[C@@H:5]([O:4][CH2:1][CH:2]=[O:37])[C@H:13]([CH3:14])[O:12][C:11]1=[O:15])[C:24](=[O:25])[O:26][C:27]([CH3:28])([CH3:29])[CH3:30])=[O:23])([CH3:21])([CH3:22])[CH3:20]

Participants

7

Reactant 4

HCID 1068Dimethyl SulfideHCID 24823OzoneHCID 516892Sodium BicarbonateHCID 86701330HCID 86701330, compound

Product 1

HCID 86701329HCID 86701329, compoundYield 907.8%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of tert-butyl N-[(3S,7S,8S,9S)-8-allyloxy-7-butoxy-9-methyl-2-oxo-1,5-dioxonan-3-yl]-N-tert-butoxycarbonylcarbamate (0.350 g, 0.698 mmol) and NaHCO3 (5.86 mg, 0.070 mmol) in MeOH (0.21 ml) and DCM (6.8 ml) was treated with ozone at −78° C. until the solution became light blue in color. The mixture was purged with nitrogen until colorless and quenched by the addition of DMS (0.10 ml, 1.40 mmol). The reaction mixture was slowly warmed to room temperature and stirred for 20 h. The mixture was concentrated and purified by flash chromatography on (SiO2, hexanes/EtOAc gradient) to yield the title compound as a colorless oil (320 mg, 91%): IR (neat) 2934, 2876, 1743, 1706, 1367, 1253, 1121, 1096 cm−1; 1H NMR (400 MHz, CDCl3) δ 9.63 (s, 1H), 5.18 (dd, J=8.9, 3.8 Hz, 1H), 4.84 (dq, J=9.4, 6.3 Hz, 1H), 4.39 (dd, J=17.9, 0.9 Hz, 1H), 4.22 (dd, J=17.8, 0.5 Hz, 1H), 4.19 (dd, J=12.2, 3.8 Hz, 1H), 3.91-3.75 (m, 2H), 3.57-3.42 (m, 2H), 3.37 (dt, J=9.2, 6.5 Hz, 1H), 3.29 (dd, J=7.9, 6.9 Hz, 1H), 3.21 (t, J=9.0 Hz, 1H), 1.52-1.40 (m, 2H), 1.45 (s, 18H), 1.41 (d, J=6.3 Hz, 3H), 1.30-1.19 (m, 2H), 0.83 (t, J=7.3 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 200.51, 168.79, 152.61, 86.19, 83.52, 83.08, 79.09, 75.35, 72.95, 71.99, 70.03, 57.92, 32.02, 27.94, 19.29, 18.84, 13.85; HRMS-ESI (m/z) [M]+ calcd for C24H41NO10, 503.2730; found, 503.2727.

Workup

  1. customThe mixture was purged with nitrogen until colorless and
  2. concentrationThe mixture was concentrated
  3. custompurified by flash chromatography on (SiO2, hexanes/EtOAc gradient)

Sources & evidence

ORD record
ord-0fc51ddd90e94a08828f1897899a4561
Source dataset
uspto-grants-2015_09
Patent number
US09144239B2

Reaction notes

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