Trimethylsilyldiazomethane → HCID 68311037, compound

HRID 529586Notes

Reaction equation

HRID 529586 reaction equation
[Si](C=[N+]=[N-])(C)(C)[CH3:2].[CH2:8]([C@H:15]([C:42]([NH:44][C@H:45]1[CH2:51][CH2:50][S:49][C@H:48]2[CH2:52][CH2:53][CH2:54][C@@H:55]([C:56]([O:58][CH3:59])=[O:57])[N:47]2[C:46]1=[O:60])=[O:43])[CH2:16][CH2:17][C@@H:18]([C:23](=[O:41])[NH:24][C@H:25]1[CH2:31][CH2:30][S:29][C@H:28]2[CH2:32][CH2:33][CH2:34][C@@H:35]([C:36]([O:38][CH3:39])=[O:37])[N:27]2[C:26]1=[O:40])[CH2:19][C:20]([OH:22])=[O:21])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C(Cl)Cl.CO>[CH2:8]([C@H:15]([C:42]([NH:44][C@H:45]1[CH2:51][CH2:50][S:49][C@H:48]2[CH2:52][CH2:53][CH2:54][C@@H:55]([C:56]([O:58][CH3:59])=[O:57])[N:47]2[C:46]1=[O:60])=[O:43])[CH2:16][CH2:17][C@H:18]([CH2:19][C:20]([O:22][CH3:2])=[O:21])[C:23]([NH:24][C@H:25]1[CH2:31][CH2:30][S:29][C@H:28]2[CH2:32][CH2:33][CH2:34][C@@H:35]([C:36]([O:38][CH3:39])=[O:37])[N:27]2[C:26]1=[O:40])=[O:41])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

5

Reactant 2

HCID 167693TrimethylsilyldiazomethaneHCID 68310550HCID 68310550, compound

Product 1

HCID 68311037HCID 68311037, compoundYield 91%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

TMS-diazomethane (2.0 M in ether, 0.0061 mL, 0.012 mmol) was added to a solution of (3R,6R)-6-benzyl-7-((4S,7S,10aS)-7-(methoxycarbonyl)-5-oxooctahydro-2H-pyrido[2,1-b][1,3]thiazepin-4-ylamino)-3-((4S,7S,10aS)-7-(methoxycarbonyl)-5-oxooctahydro-2H-pyrido[2,1-b][1,3]thiazepin-4-ylcarbamoyl)-7-oxoheptanoic acid (5.4 mg, 7.0 mmol) in DCM (0.06 mL) and MeOH (0.0062 mL). Gas evolution occurred. The reaction was stirred at rt for 1 hr. The reaction mixture was concentrated and triturated with hexanes. The solid was dried over vacuum to give methyl (4S,7S,10aS)-4-(((2R,5R)-5-benzyl-6-(((4S,7S,10aS)-7-(methoxycarbonyl)-5-oxooctahydro-7H-pyrido[2,1-b][1,3]thiazepin-4-yl)amino)-2-(2-methoxy-2-oxoethyl)-6-oxohexanoyl)amino)-5-oxooctahydro-7H-pyrido[2,1-b][1,3]thiazepine-7-carboxylate (5.0 mg, 0.0063 mmol, 91% yield) as a white solid. Anal. Calcd. for C38H52N4O10S2 m/z 788.7. found: 789.2 (M+H)+; 1H NMR (400 MHz, CDCl3) δ ppm 7.32 (1H, d), 7.25-7.21 (2H, m), 7.19-7.11 (3H, m), 7.00 (1H, d), 5.39 (1H, t, J=4.7 Hz), 5.36 (1H, t, J=4.7 Hz), 5.21-5.16 (1H, m), 5.16-5.12 (1H, m), 5.10-4.98 (2H, m), 3.72 (3H, s), 3.69 (3H, s), 3.65 (3H, s), 3.28-3.10 (2H, m), 2.98-2.81 (3H, m), 2.77-2.62 (3H, m), 2.47-2.37 (3H, m), 2.34 (1H, dd, J=15.7, 3.6 Hz), 2.27-2.19 (1H, m), 2.08-1.95 (4H, m), 1.88 (1H, ddd, J=10.9, 7.0, 3.6 Hz), 1.76-1.47 (12H, m).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. customtriturated with hexanes
  3. customThe solid was dried over vacuum

Sources & evidence

ORD record
ord-e3a7fa9a9f0a41e39c8732731840e35b
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

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