Dichloromethane → HCID 12136230, compound

HRID 857959Notes

Reaction equation

HRID 857959 reaction equation
C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.C[N+](C)(C)C.[NH2:19][C:20]([O:22][CH:23]([CH:80]([CH3:90])[CH2:81][O:82][CH2:83][C:84]1[CH:89]=[CH:88][CH:87]=[CH:86][CH:85]=1)[CH:24]([CH3:79])[CH:25]([O:71][Si:72]([C:75]([CH3:78])([CH3:77])[CH3:76])([CH3:74])[CH3:73])[CH:26]([CH3:70])[CH2:27][C:28]([CH3:69])=[CH:29][CH:30]([CH3:68])[CH:31]([O:60][Si:61]([C:64]([CH3:67])([CH3:66])[CH3:65])([CH3:63])[CH3:62])[CH:32]([CH3:59])[CH:33]=[CH:34][CH:35]([OH:58])[CH2:36][C:37](=[O:57])[CH:38]([CH3:56])[CH:39]([O:48][Si:49]([C:52]([CH3:55])([CH3:54])[CH3:53])([CH3:51])[CH3:50])[CH:40]([CH3:47])[C:41]([N:43]([O:45][CH3:46])[CH3:44])=[O:42])=[O:21].[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+].C(Cl)Cl>CC#N.CC(O)=O.CC#N>[NH2:19][C:20]([O:22][C@@H:23]([C@@H:80]([CH3:90])[CH2:81][O:82][CH2:83][C:84]1[CH:89]=[CH:88][CH:87]=[CH:86][CH:85]=1)[C@@H:24]([CH3:79])[C@H:25]([O:71][Si:72]([C:75]([CH3:78])([CH3:77])[CH3:76])([CH3:73])[CH3:74])[C@@H:26]([CH3:70])[CH2:27]/[C:28](/[CH3:69])=[CH:29]\[C@H:30]([CH3:68])[C@@H:31]([O:60][Si:61]([C:64]([CH3:65])([CH3:66])[CH3:67])([CH3:63])[CH3:62])[C@@H:32]([CH3:59])/[CH:33]=[CH:34]\[C@@H:35]([OH:58])[CH2:36][C@H:37]([OH:57])[C@H:38]([CH3:56])[C@H:39]([O:48][Si:49]([C:52]([CH3:55])([CH3:54])[CH3:53])([CH3:50])[CH3:51])[C@@H:40]([CH3:47])[C:41]([N:43]([O:45][CH3:46])[CH3:44])=[O:42])=[O:21]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 9357Potassium Sodium TartrateHCID 13696215Tetramethylammonium Triacetoxyborohydride (>90%)HCID 72415837HCID 72415837, compound

Product 1

HCID 12136230HCID 12136230, compoundYield 80%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 22391770Acetonitrile aceticacidSolvent

Conditions

Temperature
-30 °C

Procedure

A solution of tetramethylammonium triacetoxyborohydride (263 mg, 1 mmol, 10 eq) in MeCN/HOAc(1:1, 1.1 mL) is stirred for 1 h at 23° C. and cooled to −30° C. A solution of (2R,3S,4R,7S,8Z,10S, 11S,12S,13Z, 16S,17R,18R, 19S,20S)-19-[(aminocarbonyl)oxy]-3,11,17-tris[[(1,1-dimethylethyl)dimethylsilyl]oxy]-7-hydroxy-N-methoxy-N,2,4,10,12,14,16,18,20-nonamethyl-5-oxo-21-(phenylmethoxy)-8,13-heneicosadienamide (103 mg, 0.1 mmol)in MeCN (1 mL) is added dropwise. The mixture is stirred for 14 h at −30° C. Saturated Rochelle's salt solution is added and the resultant stirred for 30 min. Then the mixture is warmed to 23° C. CH2Cl2 (5 mL) is added to the mixture. The organic layer is separated, washed with brine and dried over MgSO4. The solvent is removed. The crude product is chromatographed (20% EtOAc in hexane) to give 80 mg (80%) of the desired compound as a colorless oil.

Workup

  1. stirringthe resultant stirred for 30 min
  2. temperatureThen the mixture is warmed to 23° C
  3. customThe organic layer is separated
  4. washwashed with brine
  5. dry with materialdried over MgSO4
  6. customThe solvent is removed
  7. customThe crude product is chromatographed (20% EtOAc in hexane)

Sources & evidence

ORD record
ord-7fadd7e1312b40efa21756046f9bac2b
Source dataset
uspto-grants-2006_12
Patent number
US07148218B2

Reaction notes

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