HCID 131734627, compound → HCID 131734629, compound

HRID 1770373Notes

Reaction equation

HRID 1770373 reaction equation
[C:1]([O:5][C:6]([NH:8]/[C:9](=[CH:20]\[CH2:21][CH2:22][C@H:23]([O:42][CH2:43][CH2:44][CH3:45])[C@H:24]([C@@H:30]([O:32][CH2:33][C:34]1[CH:39]=[CH:38][C:37]([O:40][CH3:41])=[CH:36][CH:35]=1)[CH3:31])[CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])/[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2]>CO>[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:20][CH2:21][CH2:22][C@H:23]([O:42][CH2:43][CH2:44][CH3:45])[C@H:24]([C@@H:30]([O:32][CH2:33][C:34]1[CH:39]=[CH:38][C:37]([O:40][CH3:41])=[CH:36][CH:35]=1)[CH3:31])[CH2:25][CH2:26][CH:27]([CH3:29])[CH3:28])[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

3

Reactant 1

HCID 131734627HCID 131734627, compound

Product 1

HCID 131734629HCID 131734629, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A solution of (6S,7S,Z)-benzyl 2-((tert-butoxycarbonyl)amino)-7-((S)-1-((4-methoxybenzyl)oxy)ethyl)-10-methyl-6-propoxyundec-2-enoate (1.50 g, 2.40 mmol) in MeOH (9.59 mL) was added to a 45 mL pressure reactor. The system was purged with N2 for 5 min and then (+)-1,2-bis((2S,5S)-2,5-diethylphospholano)benzene(1,5-cyclooctadiene)rhodium (I) trifluoromethanesulfonate (0.0170 g, 0.0240 mmol) was added. The system was purged with hydrogen gas (200 psi) 3 times, charged to 200 psi with hydrogen gas, and stirred at room temperature for 24 h. The hydrogen was evacuated and the solution was transferred to a round bottom flask rinsing with EtOAc (10 mL), and the solvent was removed under reduced pressure. The residue was dissolved in DCM (10 mL) and the resulting solution was treated with Celite® (3 scoopula tip-fulls). The solvent was removed under reduced pressure and the resulting adsorbed material was directly loaded onto a column and purified using flash column chromatography (40 g SiO2, 0→40% EtOAc/hexanes) to afford the title compound (1.10 g, 1.752 mmol, 73%) as a colorless oil: 1H NMR (400 MHz, CDCl3) δ 7.38-7.27 (m, 5H), 7.29-7.21 (m, 2H), 6.90-6.83 (m, 2H), 5.21-5.09 (m, 2H), 5.04 (d, J=8.4 Hz, 1H), 4.47 (d, J=11.3 Hz, 1H), 4.41-4.27 (m, 2H), 3.78 (s, 3H), 3.63-3.52 (m, 1H), 3.38-3.26 (m, 3H), 1.87-1.74 (m, 1H), 1.70-1.17 (m, 22H), 1.16 (d, J=6.2 Hz, 3H), 0.92-0.83 (m, 9H); 13C NMR (101 MHz, CDCl3) δ 172.75, 158.98, 155.35, 135.47, 131.30, 129.09, 128.57, 128.35, 128.20, 113.70, 79.78, 75.02, 71.89, 69.98, 66.92, 55.24, 53.59, 46.51, 38.66, 32.83, 31.98, 28.69, 28.33, 23.83, 23.54, 22.66, 22.64, 22.22, 17.13, 10.84; ESIMS m/z 650 ([M+Na]+).

Workup

  1. customThe system was purged with N2 for 5 min
  2. customThe system was purged with hydrogen gas (200 psi) 3 times
  3. additioncharged to 200 psi with hydrogen gas
  4. customThe hydrogen was evacuated
  5. customthe solution was transferred to a round bottom flask
  6. washrinsing with EtOAc (10 mL)
  7. customthe solvent was removed under reduced pressure
  8. dissolutionThe residue was dissolved in DCM (10 mL)
  9. additionthe resulting solution was treated with Celite® (3 scoopula tip-fulls)
  10. customThe solvent was removed under reduced pressure
  11. custompurified

Sources & evidence

ORD record
ord-d7742ff9e8794112b9f5f46e0e00a058
Source dataset
uspto-grants-2016_02
Patent number
US09247741B2

Reaction notes

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