Bromotrimethylsilane → HCID 173005385, compound

HRID 420441Notes

Reaction equation

HRID 420441 reaction equation
[C:1]([CH2:4][O:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]2[C:13]3[NH:17][C:16]([CH:18]=[C:19]4[N:54]=[C:22]([C:23]([CH:35]([CH2:45][CH2:46][O:47][P:48]([O:52]C)([O:50]C)=[O:49])[CH2:36][CH2:37][O:38][P:39]([O:43]C)([O:41]C)=[O:40])=[C:24]5[NH:34][C:27](=[CH:28][C:29]6[CH:30]=[CH:31][C:32]=2[N:33]=6)[CH:26]=[CH:25]5)[CH:21]=[CH:20]4)=[CH:15][CH:14]=3)=[CH:8][CH:7]=1)([OH:3])=[O:2].[Si](Br)(C)(C)C>C(Cl)Cl>[C:1]([CH2:4][O:5][C:6]1[CH:7]=[CH:8][C:9]([C:12]2[C:13]3[NH:17][C:16]([CH:18]=[C:19]4[N:54]=[C:22]([C:23]([CH:35]([CH2:36][CH2:37][O:38][P:39]([OH:43])([OH:41])=[O:40])[CH2:45][CH2:46][O:47][P:48]([OH:52])([OH:50])=[O:49])=[C:24]5[NH:34][C:27](=[CH:28][C:29]6[CH:30]=[CH:31][C:32]=2[N:33]=6)[CH:26]=[CH:25]5)[CH:21]=[CH:20]4)=[CH:15][CH:14]=3)=[CH:10][CH:11]=1)([OH:3])=[O:2]

Participants

4

Reactant 2

HCID 76113BromotrimethylsilaneHCID 178502989HCID 178502989, compound

Product 1

HCID 173005385HCID 173005385, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A sample of thoroughly dried 13a (11.8 mg, 0.015 mmol) was dissolved in dry CH2Cl2 (2.0 mL) and then treated with TMS-Br (100 μL, 0.760 mmol). The reaction mixture was stirred at room temperature for 3 h under argon. The solvents were evaporated at reduced pressure. The residue was dissolved in MeOH (3.0 mL). The solution was stirred for 1 h at room temperature. The volatile components were evaporated. The solid residue was dissolved in ˜0.2 mL aqueous NaOH (15 wt %), and the sample was diluted to ˜3 mL with water. The sample was chromatographed (silica C-18, water/MeOH, 0→50%) to afford a dark red solid (8.2 mg, 76%): 1H NMR δ (D2O) 3.61 (m, 4H), 3.95 (m, 2H), 4.33 (m, 2H), 5.04 (s, 2H), 5.89 (m, 1H), 7.57 (d, J=7.8 Hz, 2H), 7.94-7.97 (m, 2H), 8.91 (m, 2H), 9.28-9.34 (m, 2H), 9.78-9.82 (m, 2H), 10.24-10.33 (m, 4H); ESI-MS obsd (+) 362.1 (M+2H)2+, 723.1 (M+H)+, 745.1 (M+Na)+ (−) 721.1 (M−H)−, calcd 722.15 (M, M=C33H32N4O11P2); λabs 402, 506 nm; λem (λexc 402 mm) 628, 688 nm; HPLC (20% B, 1.5 mL/min, tR=2.22 min).

Workup

  1. customThe solvents were evaporated at reduced pressure
  2. dissolutionThe residue was dissolved in MeOH (3.0 mL)
  3. stirringThe solution was stirred for 1 h at room temperature
  4. customThe volatile components were evaporated
  5. dissolutionThe solid residue was dissolved in ˜0.2 mL aqueous NaOH (15 wt %)
  6. additionthe sample was diluted to ˜3 mL with water
  7. customThe sample was chromatographed (silica C-18, water/MeOH, 0→50%)

Sources & evidence

ORD record
ord-3d4896ddc1ee40a3b4c2dca37d54c2cb
Source dataset
uspto-grants-2012_01
Patent number
US08097609B2

Reaction notes

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