m-Chloroperbenzoic acid → HCID 87366534, compound

HRID 1670051Notes

Reaction equation

HRID 1670051 reaction equation
[CH2:1]([P:8]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])(N(C(C)C)C(C)C)([O-:10])[O-:9])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:36]([O:43][C@H:44]1[C@@H:49]([O:50][CH2:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[C@H:48]([O:58][CH2:59][C:60]2[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=2)[C@@H:47]([CH2:66][O:67][CH2:68][C:69]2[CH:74]=[CH:73][CH:72]=[CH:71][CH:70]=2)[O:46][C@@H:45]1[O:75][CH2:76][CH:77]([CH2:79][O:80][C@H:81]1[O:110][C@H:109]([CH2:111][O:112][CH2:113][C:114]2[CH:119]=[CH:118][CH:117]=[CH:116][CH:115]=2)[C@@H:100]([O:101][CH2:102][C:103]2[CH:108]=[CH:107][CH:106]=[CH:105][CH:104]=2)[C@H:91]([O:92][CH2:93][C:94]2[CH:99]=[CH:98][CH:97]=[CH:96][CH:95]=2)[C@@H:82]1[O:83][CH2:84][C:85]1[CH:90]=[CH:89][CH:88]=[CH:87][CH:86]=1)O)[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1.N1C=NN=N1.C1C=C(Cl)C=C(C(OO)=O)C=1>ClCCl>[CH2:1]([P:8]([O:9][CH:77]([CH2:79][O:80][C@H:81]1[O:110][C@H:109]([CH2:111][O:112][CH2:113][C:114]2[CH:119]=[CH:118][CH:117]=[CH:116][CH:115]=2)[C@@H:100]([O:101][CH2:102][C:103]2[CH:104]=[CH:105][CH:106]=[CH:107][CH:108]=2)[C@H:91]([O:92][CH2:93][C:94]2[CH:95]=[CH:96][CH:97]=[CH:98][CH:99]=2)[C@@H:82]1[O:83][CH2:84][C:85]1[CH:86]=[CH:87][CH:88]=[CH:89][CH:90]=1)[CH2:76][O:75][C@H:45]1[O:46][C@H:47]([CH2:66][O:67][CH2:68][C:69]2[CH:74]=[CH:73][CH:72]=[CH:71][CH:70]=2)[C@@H:48]([O:58][CH2:59][C:60]2[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=2)[C@H:49]([O:50][CH2:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)[C@@H:44]1[O:43][CH2:36][C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=1)([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 87367150HCID 87367150, compoundHCID 131729087HCID 131729087, compoundHCID 178418441HCID 178418441, compound

Product 1

HCID 87366534HCID 87366534, compoundYield 64.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of the phosphoramidite 45 (54 mg, 0.105 mmol) in dichloromethane (12 mL) was cannulated onto a mixture of the alcohol 12 (80 mg, 0.070 mmol) and 1H-tetrazole (11 mg, 0.161 mmol) under argon. The reaction mixture was stirred at RT for 2 hrs then cooled in ice when a solution of MCPBA (75%, 25 mg, 0.141 mmol), pre-dried for 20 min over MgSO4, was added to the reaction mixture. After a further 1 hr the reaction mixture was diluted with dichloromethane (30 mL) and quenched with the addition of 10% aqueous Na2S2O3 (45 mL). The aqueous phase was further extracted with dichloromethane (35 mL) and the combined organic extract washed with sat. NaHCO3 (2×40 mL) and dried (MgSO4). After filtration the solvent was removed at reduced pressure to give the crude product that was purified by column chromatography on silica gel. Gradient elution with ethyl acetate/petroleum ether (10:90→30:70) afforded the title compound 46 (70 mg, 0.045 mmol, 64%) as a thin film; [α]D18 +31 (c 0.54, CHCl3); 1H NMR (300 MHz, CDCl3) δ 7.40-7.10 (m, 45H), 4.97-4.40 (m, 21H), 4.00-3.55 (m, 18H), 1.51-1.42 (m, 2H), 1.30-1.15 (m, 30H), 0.88-0.81 (m, 3H); 13C NMR (75 MHz, CDCl3) δ 138.8, 128.9, 128.7, 128.3, 128.1, 127.9, 127.9, 99.0, 98.4, 80.6, 75.9, 75.4, 75.2, 75.1, 73.7, 73.0, 72.6, 72.4, 69.5, 68.5, 67.2, 66.9, 32.3, 30.6, 30.5, 30.1, 29.9, 29.7, 29.6, 25.8, 23.1, 14.5; 31P NMR (121.2 MHz, CDCl3) δ −0.12; HRMS-ESI (+ve) (Found: m/z 1576.8426 (MNH4+), C96H123NO16P requires m/z 1576.8579).

Workup

  1. dry with materialpre-dried for 20 min over MgSO4
  2. additionwas added to the reaction mixture
  3. additionAfter a further 1 hr the reaction mixture was diluted with dichloromethane (30 mL)
  4. customquenched with the addition of 10% aqueous Na2S2O3 (45 mL)
  5. extractionThe aqueous phase was further extracted with dichloromethane (35 mL)
  6. extractionthe combined organic extract
  7. washwashed with sat. NaHCO3 (2×40 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationAfter filtration the solvent
  10. customwas removed at reduced pressure
  11. customto give the crude product that
  12. customwas purified by column chromatography on silica gel
  13. washGradient elution with ethyl acetate/petroleum ether (10:90→30:70)

Sources & evidence

ORD record
ord-ef2be75cff0948d4b1a0dc9bfd9faf3f
Source dataset
uspto-grants-2011_08
Patent number
US07989602B2

Reaction notes

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