Myristic Acid → tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl ester

HRID 2224023Notes

Reaction equation

HRID 2224023 reaction equation
[C:1]([OH:16])(=[O:15])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14].Cl.C(N=C=NCCCN(C)C)C.[CH3:29][C:30]([CH3:65])([CH3:64])/[CH:31]=[CH:32]/[C@H:33]1[O:38][C:37]([CH3:40])([CH3:39])[O:36][C@@H:35]([C@@H:41]([O:61][CH3:62])[C:42]([NH:44][C@H:45]2[CH2:51][CH2:50][C@@H:49](O)[CH2:48][N:47]([CH2:53][C:54]3[CH:55]=[N:56][CH:57]=[CH:58][CH:59]=3)[C:46]2=[O:60])=[O:43])[C@@H:34]1[OH:63]>CN(C)C1C=CN=CC=1.C(Cl)Cl>[CH3:29][C:30]([CH3:65])([CH3:64])/[CH:31]=[CH:32]/[C@H:33]1[O:38][C:37]([CH3:39])([CH3:40])[O:36][C@@H:35]([C@@H:41]([O:61][CH3:62])[C:42]([NH:44][C@@H:45]2[C:46](=[O:60])[N:47]([CH2:53][C:54]3[CH:55]=[N:56][CH:57]=[CH:58][CH:59]=3)[CH2:48][C@H:49]([O:15][C:1](=[O:16])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])[CH2:50][CH2:51]2)=[O:43])[C@@H:34]1[OH:63]

Participants

6

Reactant 3

HCID 11005Myristic AcidHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 69266165(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-N-((3S,6R)-6-hydroxy-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl)-2-methoxy-acetamide

Product 1

HCID 86609576tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl esterYield 29.4%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of tetradecanoic acid (0.39 g 1.7 mmol) and 4-dimethylaminopyridine (0.21 g, 1.7 mmol) in CH2Cl2(15 mL) is added 1-ethyl-3-[3-(dimethylamino)propyl]-carbodiimidehydrochloride (0.34 g, 1.7 mmol) at room temperature. After 30 min (R)-2-[(4R,5R,6R)-6-((E)3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-N-((3S,6R)-6-hydroxy-2-oxo-1-pyridin-3-ylmethyl-azepan-3-yl)-2-methoxy-acetamide (0.74 g, 1.4 mmol) is added and stirred for 16 h. The reaction is concentrated and chromatographed on silica (98% CH2Cl2/2% CH3OH) to give 0.3 g (28.8%) of tetradecanoic acid (3R,6S)-6-{(R)-2-[(4R,5R,6R)-6-((E)-3,3-dimethyl-but-1-enyl)-5-hydroxy-2,2-dimethyl-[1,3]dioxan-4-yl]-2-methoxy-acetylamino}-7-oxo-1-pyridin-3-ylmethyl-azepan-3-yl ester as a white solid. 1H NMR 300 MHz δ 8.54(s, 2H), 7.88 (d, 1H), 7.63 (d, 1H), 7.29 (m, 1H), 5.77 (d, 1H), 5.54(dd, 1H), 5.06 (d, 1H), 4.75 (m, 1H), 4.50 (m, 1H), 4.29 (m, 2H), 4.08 (d, 1H), 3.90 (d, 1H), 3.52 (s, 3H), 3.50 (m, 1H), 3.25 (d, 1H), 2.27 (t, 2H), 2.15 (m, 2H), 2.00 (m, 1H), 1.60 (m, 3H), 1.46 (d, 2H), 1.25 (m, 24H), 1.04 (s, 9H), 0.88 (t, 3H); MS (ESI) 730.3 (M+H)+.

Workup

  1. concentrationThe reaction is concentrated
  2. customchromatographed on silica (98% CH2Cl2/2% CH3OH)

Sources & evidence

ORD record
ord-b2988b99bd0442268e4c2d06b744db18
Source dataset
uspto-grants-2008_05
Patent number
US07378410B2

Reaction notes

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