Tacrolimus-13C,D2 → HCID 57266865, compound

HRID 973703Notes

Reaction equation

HRID 973703 reaction equation
[CH2:1]([CH:4]1[CH:30]=[C:29]([CH3:31])[CH2:28][CH:27]([CH3:32])[CH2:26][CH:25]([O:33][CH3:34])[CH:24]2[O:35][C:20]([OH:39])([CH:21]([CH3:38])[CH2:22][CH:23]2[O:36][CH3:37])[C:19](=[O:40])[C:18](=[O:41])[N:17]2[CH:12]([CH2:13][CH2:14][CH2:15][CH2:16]2)[C:11](=[O:42])[O:10][CH:9]([C:43]([CH3:54])=[CH:44][CH:45]2[CH2:50][CH2:49][CH:48]([OH:51])[CH:47]([O:52][CH3:53])[CH2:46]2)[CH:8]([CH3:55])[CH:7]([OH:56])[CH2:6][C:5]1=[O:57])[CH:2]=[CH2:3].[BH4-].[Na+]>CO.C(O)(C)C>[CH2:1]([CH:4]1[CH:30]=[C:29]([CH3:31])[CH2:28][CH:27]([CH3:32])[CH2:26][CH:25]([O:33][CH3:34])[CH:24]2[O:35][C:20]([OH:39])([CH:21]([CH3:38])[CH2:22][CH:23]2[O:36][CH3:37])[CH:19]([OH:40])[C:18](=[O:41])[N:17]2[CH:12]([CH2:13][CH2:14][CH2:15][CH2:16]2)[C:11](=[O:42])[O:10][CH:9]([C:43]([CH3:54])=[CH:44][CH:45]2[CH2:50][CH2:49][CH:48]([OH:51])[CH:47]([O:52][CH3:53])[CH2:46]2)[CH:8]([CH3:55])[CH:7]([OH:56])[CH2:6][C:5]1=[O:57])[CH:2]=[CH2:3]

Participants

5

Reactant 2

HCID 5372Tacrolimus-13C,D2HCID 4311764Sodium borohydride

Product 1

HCID 57266865HCID 57266865, compoundYield 42.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3776IsopropanolSolvent

Procedure

To a stirred solution of 17-allyl- 1,14-dihydroxy-12-[2'-(4"-hydroxy-3"-methoxycyclohexyl)1-methylvinyl]-23,25-dimethoxy-13,19,21,27-tetramethyl-11,28-dioxa-4-azatricyclo[22.3.1.04,9 ]octacos-18-ene-2,3,10,16-tetraone (300 mg, 0.374 mmol) in 9 ml MeOH was added dropwise at RT a solution of NaBH4 (0.12 mmol) in 2 ml isopropanol. After stirring at RT for 15 minutes the reaction was quenched by pouring into 1.5 ml acetic acid in ice and the mixture was extracted with ethyl acetate (3×50 ml). The combined organic layers were washed with sat. NaHCO3 (1×50 ml) and water (1×50 ml) and dried over MgSO4. Evaporation of solvent gave 320 mg of crude product which was purified by prep TLC (10% i-PrOH/CH2Cl2) to give 127 mg (42% yield) of the title compound (with NMR and mass spectra consistent with the structure).

Workup

  1. customwas quenched
  2. additionby pouring into 1.5 ml acetic acid in ice
  3. extractionthe mixture was extracted with ethyl acetate (3×50 ml)
  4. washThe combined organic layers were washed with sat. NaHCO3 (1×50 ml) and water (1×50 ml)
  5. dry with materialdried over MgSO4
  6. customEvaporation of solvent
  7. customgave 320 mg of crude product which
  8. customwas purified by prep TLC (10% i-PrOH/CH2Cl2)

Sources & evidence

ORD record
ord-f15601dbc548412b9b09c2252cfabe19
Source dataset
uspto-grants-1991_11
Patent number
US05064835

Reaction notes

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