Trifluoromethanesulfonic acid → 17-Ethyl-1,14-dihydroxy-12-[2'-(4"-(tert-butyldimethylsiloxy)-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 2226786Notes

Reaction equation

HRID 2226786 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]([CH3:59])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52])[CH:46]([OH:58])[CH2:45]2)[CH:7]([CH3:60])[CH:6]([OH:61])[CH2:5][C:4]1=[O:62])[CH3:2].ClC(Cl)(Cl)C(=N)O[CH2:67][CH:68]=[CH2:69].FC(F)(F)S(O)(=O)=O>C(OCC)(=O)C>[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]([CH3:59])=[CH:43][CH:44]2[CH2:49][CH2:48][CH:47]([O:50][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52])[CH:46]([O:58][CH2:69][CH:68]=[CH2:67])[CH2:45]2)[CH:7]([CH3:60])[CH:6]([OH:61])[CH2:5][C:4]1=[O:62])[CH3:2]

Participants

5

Reactant 3

HCID 62406Trifluoromethanesulfonic acidHCID 316905Allyl 2,2,2-TrichloroacetimidateHCID 5715677017-Ethyl-1,14-dihydroxy-12-[2'-(4"-(tert-butyldimethylsiloxy)-3 "-hydroxycyclohexyl)-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 1

HCID 5713502317-Ethyl-1,14-dihydroxy-12-[2'-(4"-(tert-butyldimethylsiloxy)-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 49.5%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 17-ethyl-1,14-dihydroxy-12-[2'-(4"-(tert-butyldimethylsiloxy)-3"-hydroxycyclohexyl)-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 (290 mg in 3.9 ml 33% methylene chloride in cyclohexane) allyl trichloroacetimidate (131 mg neat) was added and the reagents allowed to mix for 5 minutes. Trifluoromethanesulfonic acid (6 μl neat) was added slowly via syringe and the mixture stirred at room temperature. After 5 days the reaction was diluted with ethyl acetate and quenched with saturated sodium bicarbonate. The layers were separated, and the organic layer was washed with brine then dried over magnesium sulfate. Purification of the concentrate by preparative TLC on silica gel (ethyl acetate:hexane (1:5)+1% methanol) gave the title compound (150 mg). 1H NMR consistent with the desired structure.

Workup

  1. additionto mix for 5 minutes
  2. customquenched with saturated sodium bicarbonate
  3. customThe layers were separated
  4. washthe organic layer was washed with brine
  5. dry with materialthen dried over magnesium sulfate
  6. customPurification of the
  7. concentrationconcentrate by preparative TLC on silica gel (ethyl acetate:hexane (1:5)+1% methanol)

Sources & evidence

ORD record
ord-7767d7eb9d504f21baac6ab1ab48a24c
Source dataset
uspto-grants-1994_09
Patent number
US05349061

Reaction notes

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