Triphenylphosphine → 17-Ethyl-1-hydroxy-12-[2'-(4 "-amino-3"-allyloxycyclohexyl)-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

HRID 373278Notes

Reaction equation

HRID 373278 reaction equation
[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:57])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([N:50]=[N+]=[N-])[CH:46]([O:53][CH2:54][CH:55]=[CH2:56])[CH2:45]2)[CH:7]([CH3:58])[CH2:6][CH2:5][C:4]1=[O:59])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC=CC=1>[OH-:9].[NH4+:16].[CH2:1]([CH:3]1[CH:29]=[C:28]([CH3:30])[CH2:27][CH:26]([CH3:31])[CH2:25][CH:24]([O:32][CH3:33])[CH:23]2[O:34][C:19]([OH:38])([CH:20]([CH3:37])[CH2:21][CH:22]2[O:35][CH3:36])[C:18](=[O:39])[C:17](=[O:40])[N:16]2[CH:11]([CH2:12][CH2:13][CH2:14][CH2:15]2)[C:10](=[O:41])[O:9][CH:8]([C:42]([CH3:57])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([NH2:50])[CH:46]([O:53][CH2:54][CH:55]=[CH2:56])[CH2:45]2)[CH:7]([CH3:58])[CH2:6][CH2:5][C:4]1=[O:59])[CH3:2]

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 8674633217-Ethyl-1-hydroxy-12-[2'-(4"-azido-3"-allyloxycyclohexyl)-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

Product 2

HCID 14923Ammonium HydroxideYield 2%HCID 7737294017-Ethyl-1-hydroxy-12-[2'-(4 "-amino-3"-allyloxycyclohexyl)-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-tetraoneYield 130.5%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 17-ethyl-1-hydroxy-12-[2'-(4"-azido-3"-allyloxycyclohexyl)-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 (25 mg) in 10% aqueous benzene (850 μl) was added triphenylphosphine (12 mg) and the mixture heated to 70° C. with stirring. After 15 hours, the stir bar was removed and the reaction cooled to room temperature. The mixture was concentrated to 10% volume in vacuo and applied directly to a column of silica gel for purification by flash chromatography (ethyl acetate:hexane (1:1)+1% methanol then 2% ammonium hydroxide, 5% methanol in methylene chloride) to give the title compound (15.8 mg).

Workup

  1. customthe stir bar was removed
  2. temperaturethe reaction cooled to room temperature
  3. concentrationThe mixture was concentrated to 10% volume in vacuo
  4. customapplied directly to a column of silica gel for purification by flash chromatography (ethyl acetate:hexane (1:1)+1% methanol

Sources & evidence

ORD record
ord-91a4aeb5c5b24bbb8170677335b6f8d2
Source dataset
uspto-grants-1992_11
Patent number
US05162334

Reaction notes

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