HCID 5372, compound → 17-Allyl-1-hydroxy-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]octacosa-14,18-diene-2,3,10,16-tetraone

HRID 248256Notes

Reaction equation

HRID 248256 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](O)[CH2:6][C:5]1=[O:57])[CH:2]=[CH2:3].C1(C)C=CC(S(O)(=O)=O)=CC=1>C1C=CC=CC=1>[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]=[CH:6][C:5]1=[O:57])[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 5372HCID 5372, compoundHCID 6101p-Toluenesulfonic acid

Product 1

HCID 5715345717-Allyl-1-hydroxy-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]octacosa-14,18-diene-2,3,10,16-tetraoneYield 92.1%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A 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 (800 mg) and a catalytic amount of p-toluenesulfonic acid in 40 ml of dry benzene was refluxed for 1.5 h under nitrogen atmosphere. The solvent was removed under reduced pressure and the dark brown residue was purified by column chromatography on silica gel (eluted with ether) to give 720 mg of 17-allyl-1-hydroxy-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-14,18-diene-2,3,10,16-tetraone as a white solid. This material (500 mg) was dissolved in dry toluene (30 ml) and to this solution was added tetrakistriphenylphosphine palladium° (50 mg) and acetic acid (50 μl) at room temperature. To this yellow solution was added tri-n-butyltin hydride (200 mg) and the mixture was stirred for 1 h. The Brown colored solution was directly applied to column chromatography on silica gel (first eluted with hexane, then with ether) to give 380 mg of the title compound.

Workup

  1. customThe solvent was removed under reduced pressure
  2. customthe dark brown residue was purified by column chromatography on silica gel (eluted with ether)

Sources & evidence

ORD record
ord-936489f1c9fb465e8e306e866704a011
Source dataset
uspto-grants-1993_05
Patent number
US05208228

Reaction notes

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