Phenyl isocyanate → 4-[9-hydroxy-2-[5-[5-[6-hydroxy-3,5-dimethyl-6-(phenylcarbamoyloxymeth yl)oxan-2-yl]-3-methyl-oxolan-2-yl]-5-methyl-oxolan-2-yl]-2,8-dimethyl -1,6-dioxaspiro[4.5]dec-7-yl]-2-methyl-3-propanoyloxy-pentanoic acid

HRID 1719672Notes

Reaction equation

HRID 1719672 reaction equation
[C:1]1([N:7]=[C:8]=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:10][CH2:11][C:12]([O:14][C@@H:15]([C@@H:54]([C:56]([OH:58])=[O:57])[CH3:55])[C@@H:16]([C@H:18]1[O:23][C@:22]2([O:27][C@@:26]([C@@H:29]3[O:33][C@@:32]([C@@H:35]4[O:39][C@@H:38]([C@H:40]5[O:45][C@@:44]([OH:48])([CH2:46][OH:47])[C@H:43]([CH3:49])[CH2:42][C@@H:41]5[CH3:50])[CH2:37][C@@H:36]4[CH3:51])([CH3:34])[CH2:31][CH2:30]3)([CH3:28])[CH2:25][CH2:24]2)[CH2:21][C@H:20]([OH:52])[C@H:19]1[CH3:53])[CH3:17])=[O:13]>N1C=CC=CC=1.ClCCl>[CH3:10][CH2:11][C:12]([O:14][CH:15]([CH:54]([C:56]([OH:58])=[O:57])[CH3:55])[CH:16]([CH:18]1[O:23][C:22]2([O:27][C:26]([CH:29]3[O:33][C:32]([CH:35]4[O:39][CH:38]([CH:40]5[O:45][C:44]([OH:48])([CH2:46][O:47][C:8]([NH:7][C:1]6[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=6)=[O:9])[CH:43]([CH3:49])[CH2:42][CH:41]5[CH3:50])[CH2:37][CH:36]4[CH3:51])([CH3:34])[CH2:31][CH2:30]3)([CH3:28])[CH2:25][CH2:24]2)[CH2:21][CH:20]([OH:52])[CH:19]1[CH3:53])[CH3:17])=[O:13]

Participants

5

Reactant 2

HCID 7672Phenyl isocyanateHCID 71454116Laidlomycin

Product 1

HCID 1277764-[9-hydroxy-2-[5-[5-[6-hydroxy-3,5-dimethyl-6-(phenylcarbamoyloxymeth yl)oxan-2-yl]-3-methyl-oxolan-2-yl]-5-methyl-oxolan-2-yl]-2,8-dimethyl -1,6-dioxaspiro[4.5]dec-7-yl]-2-methyl-3-propanoyloxy-pentanoic acidYield 61.1%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

Phenyl isocyanate (2.38 g, 20 mmol) was added to a solution of laidlomycin (14 g, 20 mmol) in 100 ml of pyridine. The mixture was heated in an oil bath at 70° for 30 min. The mixture was cooled, diluted with dichloromethane, washed with 5% aqueous hydrochloric acid and water, and evaporated. The residue was purified by silica gel chromatography (75% ether hexane, 0.01% formic acid eluent) to afford 10 g of laidlomycin phenylcarbamate as an amorphous solid which melted at 88°-90° C. Carbon-13 NMR spectroscopy confirmed the structure.

Workup

  1. temperatureThe mixture was heated in an oil bath at 70° for 30 min
  2. temperatureThe mixture was cooled
  3. washwashed with 5% aqueous hydrochloric acid and water
  4. customevaporated
  5. customThe residue was purified by silica gel chromatography (75% ether hexane, 0.01% formic acid eluent)

Sources & evidence

ORD record
ord-335dc7e5dafe4226b3da5a18ea45d423
Source dataset
uspto-grants-1985_09
Patent number
US04542027

Reaction notes

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