Triacetoxyperiodinane → Relacatib

HRID 229798Notes

Reaction equation

HRID 229798 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[OH:23][C@@H:24]1[C@@H:30]([NH:31][C:32]([C@@H:34]([NH:39][C:40]([C:42]2[O:43][C:44]3[CH:50]=[CH:49][CH:48]=[CH:47][C:45]=3[CH:46]=2)=[O:41])[CH2:35][CH:36]([CH3:38])[CH3:37])=[O:33])[CH2:29][CH2:28][C@@H:27]([CH3:51])[N:26]([S:52]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][N:56]=2)(=[O:54])=[O:53])[CH2:25]1.O[C@H]1[C@H](NC([C@@H](NC(C2OC3C=CC=CC=3C=2)=O)CC(C)C)=O)CC[C@H](C)N(S(C2C=CC=CN=2)(=O)=O)C1>C(Cl)Cl>[CH3:37][CH:36]([CH3:38])[CH2:35][C@H:34]([NH:39][C:40]([C:42]1[O:43][C:44]2[CH:50]=[CH:49][CH:48]=[CH:47][C:45]=2[CH:46]=1)=[O:41])[C:32](=[O:33])[NH:31][C@H:30]1[CH2:29][CH2:28][C@@H:27]([CH3:51])[N:26]([S:52]([C:55]2[CH:60]=[CH:59][CH:58]=[CH:57][N:56]=2)(=[O:53])=[O:54])[CH2:25][C:24]1=[O:23]

Participants

5

Reactant 3

HCID 159087TriacetoxyperiodinaneHCID 16743099Benzofuran-2-carboxylic acid {(S)-1-[(3S,4S,7R)-3-hydroxy-7-methyl-1-(pyridine-2-sulfonyl)-azepan-4-ylcarbamoyl]-3-methyl-butyl}-amideHCID 69912198benzofuran-2-carboxylic acid ((S)-1-[(3R,4R,7S)-3-hydroxy-7-methyl-1-(pyridine-2-sulfonyl)-azepan-4-ylcarbamoyl]-3-methyl-butyl}-amide

Product 1

HCID 6918602Relacatib

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Dess-Martin periodinane (1.0 g, 2.36 mmol) was added to a solution of benzofuran-2-carboxylic acid {(S)-1-[(3S,4S,7R)-3-hydroxy-7-methyl-1-(pyridine-2-sulfonyl)-azepan-4-ylcarbamoyl]-3-methyl-butyl}-amide and benzofuran-2-carboxylic acid {(S)-1-[(3R,4R,7S)-3-hydroxy-7-methyl-1-(pyridine-2-sulfonyl)-azepan-4-ylcarbamoyl]-3-methyl-butyl}-amide (0.8 g, 1.48 mmol) in CH2Cl2 (20 ml) and was stirred at RT for 45 minutes. The solution was washed with 10% NaHCO3 and brine. Purification by column chromatography (60% ethyl acetate/hexanes) gave the title compound as a mixture of diasteromers (0.75 g, 94%); The diastereomers were separated by HPLC. Diastereomer 1:1H NMR: 8.72 (m, 1H), 8.0 (d, 1H), 8.92 (dd, 1H), 7.65 (d, 1H), 7.56 (d, 1H), 7.45 (s, 1H), 7.42 (dd, 2H), 7.28 (d, 1H), 7.10 (d, 1H), 5.15 (m, 1H), 4.77 (d, 1H), 4.68 (m, 1H), 4.40 (m, 1H), 3.86 (d, 1H), 2.20-2.08 (m, 2H), 1.78-1.50 (m, 5H), 1.22 (dd, 3H), 0.98 (m, 6H); Electrospray mass spec: M+H+=541.2; Diastereomer 2:1H NMR: 8.68 (m, 1H), 8.04 (d, 1H), 8.92 (dd, 1H), 7.68 (d, 1H), 7.58 (d, 2H), 7.52 (s, 1H), 7.42 (dd, 1H), 7.29 (d, 1H), 7.05 (m, 2H), 5.12 (m, 1H), 4.75-4.68 (m, 1H), 4.43 (m, 1H), 3.83 (d, 1H), 2.25-2.12 (m, 2H), 1.88-1.50 (m, 5H), 0.98 (m, 9H); Electrospray mass spec: M+H+=541.2

Workup

  1. washThe solution was washed with 10% NaHCO3 and brine
  2. customPurification by column chromatography (60% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-11ac337449a84ee5a5666d979d5c7a6e
Source dataset
uspto-grants-2009_07
Patent number
US07563784B2

Reaction notes

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