Trimethyl phosphite → HCID 178502950, compound

HRID 40536Notes

Reaction equation

HRID 40536 reaction equation
[C:1]([O:5][C:6]([CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[C:17]3[NH:21][C:20]([CH:22]=[C:23]4[N:46]=[C:26]([C:27]([CH:39]([CH2:43][CH2:44]Br)[CH2:40][CH2:41]Br)=[C:28]5[NH:38][C:31](=[CH:32][C:33]6[CH:34]=[CH:35][C:36]=2[N:37]=6)[CH:30]=[CH:29]5)[CH:25]=[CH:24]4)=[CH:19][CH:18]=3)=[CH:12][CH:11]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[O:48][P:49]([O:52][CH3:53])[O:50][CH3:51]>>[C:1]([O:5][C:6]([CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2[C:17]3[NH:21][C:20]([CH:22]=[C:23]4[N:46]=[C:26]([C:27]([CH:39]([CH2:43][CH2:44][P:49]([O:52][CH3:53])([O:50][CH3:51])=[O:48])[CH2:40][CH2:41][P:49]([O:52][CH3:53])([O:50][CH3:51])=[O:48])=[C:28]5[NH:38][C:31](=[CH:32][C:33]6[CH:34]=[CH:35][C:36]=2[N:37]=6)[CH:30]=[CH:29]5)[CH:25]=[CH:24]4)=[CH:19][CH:18]=3)=[CH:12][CH:11]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

3

Reactant 2

HCID 8472Trimethyl phosphiteHCID 173005377HCID 173005377, compound

Product 1

HCID 178502950HCID 178502950, compoundYield 65%

Procedure

A sample of 15a (38.7 mg, 0.048 mmol) was dissolved in trimethylphosphite (5.0 mL). The solution was refluxed under argon for 1.5 days. The P(OMe)3 was evaporated at reduced pressure. The residue was chromatographed (silica, CH2Cl2/MeOH, 0→5%) to yield a dark purple solid (24.6 mg, 65%): 1H NMR δ 1.64 (s, 9H), 3.15 (m, 2H), 3.32-3.36 (m, 2H), 3.43 (s, 3H), 3.47 (s, 6H), 3.50 (s, 3H), 3.81-3.87 (m, 4H), 4.84 (s, 2H), 5.44 (m, 1H), 7.35 (d, J=8.1 Hz, 2H), 8.17 (d, J=8.1 Hz, 2H), 9.10 (s, 2H), 9.40 (s, 2H), 9.50-9.51 (m, 1H), 9.73-9.74 (m, 2H), 10.30-10.31 (m, 2H); LD-MS obsd 803.7, calcd 800.3104 (C41H48N4O9P2); λabs (log ε) 407 (4.90), 504 nm; λem(λexc 407 nm) 636 nm, 702 nm. Varying amounts of a less polar purple solid (16a-Br) were isolated along with small amounts of the starting material 15a (limited characterization). Data for 16a-Br: 1H NMR δ 0.86-0.95 (m, 1H), 1.65 (s, 9H), 1.91-2.00 (m, 1H), 3.13-3.40 (m, 6H), 3.44 (s, 3H), 3.48 (s, 3H), 3.55-3.85 (m, 2H), 4.83 (s, 2H), 5.51-5.61 (m, 1H), 7.34 (d, J=8.1 Hz, 2H), 8.17 (d, J=8.1 Hz, 2H), 9.08-9.10 (m, 2H), 9.37-9.41 (m, 2H), 9.49-9.51 (m, 2H), 9.67-9.68 (m, 1H), 9.84-9.85 (m, 1H), 10.30 (s, 2H); LD-MS obsd 773.6, calcd 773.2 [(M+H)+, M=C39H42BrN4O6P2]; λabs 407, 502 nm; λem (λexc 407 nm) 634, 702 nm.

Workup

  1. temperatureThe solution was refluxed under argon for 1.5 days
  2. customThe P(OMe)3 was evaporated at reduced pressure
  3. customThe residue was chromatographed (silica, CH2Cl2/MeOH, 0→5%)

Sources & evidence

ORD record
ord-497aa2de8c6a4399aba14572840fbea3
Source dataset
uspto-grants-2013_09
Patent number
US08530459B2

Reaction notes

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