2-Methyl-6-nitrobenzoic anhydride → HCID 91667535, compound

HRID 1776100Notes

Reaction equation

HRID 1776100 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([CH2:13][CH2:14][CH2:15][C@@H:16]([C@@H:22]([O:26][Si:27]([CH:34]([CH3:36])[CH3:35])([CH:31]([CH3:33])[CH3:32])[CH:28]([CH3:30])[CH3:29])[C@@H:23]([OH:25])[CH3:24])[CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])[C:10](O)=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].CC1C=CC=C([N+]([O-])=O)C=1C(OC(C1C([N+]([O-])=O)=CC=CC=1C)=O)=O>C(Cl)Cl.CN(C1C=CN=CC=1)C>[C:1]([O:5][C:6](=[O:7])[NH:8][C@H:9]1[CH2:13][CH2:14][CH2:15][C@H:16]([CH2:17][CH2:18][CH:19]([CH3:21])[CH3:20])[C@@H:22]([O:26][Si:27]([CH:34]([CH3:36])[CH3:35])([CH:28]([CH3:29])[CH3:30])[CH:31]([CH3:32])[CH3:33])[C@H:23]([CH3:24])[O:25][C:10]1=[O:11])([CH3:3])([CH3:4])[CH3:2]

Participants

5

Reactant 2

HCID 104726482-Methyl-6-nitrobenzoic anhydrideHCID 123953362HCID 123953362, compound

Product 1

HCID 91667535HCID 91667535, compoundYield 59.1%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of (2S,6R)-2-((tert-butoxycarbonyl)amino)-6-((1R,2S)-2-hydroxy-1-((triisopropylsilyl)oxy)propyl)-9-methyldecanoic acid (7.76 g, 13.1 mmol) in anhydrous CH2Cl2 (500 mL) was added to a solution of MNBA (9.04 g, 26.3 mmol) and DMAP (12.8 g, 105.0 mmol) in anhydrous CH2Cl2 (2.5 L) at room temperature over the course of 4 h. After the addition was complete, the reaction was stirred for 12 h at room temperature, concentrated and purified by column chromatography on SiO2 (gradient, hexanes/ethyl acetate) to furnish the title product as a sticky pale yellow solid (3.98 g, 59%): 1H NMR (400 MHz, CDCl3) δ 5.14 (d, J=8.2 Hz, 1H), 4.90-4.78 (m, 1H), 4.20-4.09 (m, 1H), 3.61 (t, J=7.6 Hz, 1H), 2.26-2.10 (m, 1H), 1.79-1.65 (m, 1H), 1.65-1.40 (m, 3H), 1.44 (s, 9H), 1.37 (d, J=6.5 Hz, 3H), 1.32-0.97 (m, 28H), 0.884 (d, J=6.7 Hz, 3H), 0.878 (d, J=6.7 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 173.12, 154.92, 79.62, 78.59, 75.82, 60.33, 53.07, 45.68, 36.92, 34.17, 28.64, 28.58, 28.31, 27.27, 22.82, 22.49, 18.95, 18.86, 18.38, 18.33, 13.75; ESIMS m/z 536.5 ([M+Na]+).

Workup

  1. additionAfter the addition
  2. concentrationconcentrated
  3. custompurified by column chromatography on SiO2 (gradient, hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-62bfb5ac46e34465bff337138067e18b
Source dataset
uspto-grants-2016_02
Patent number
US09265253B2

Reaction notes

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