Triphenylphosphine → allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate

HRID 1596731Notes

Reaction equation

HRID 1596731 reaction equation
[CH2:1]([O:4][C:5]([O:7][C@@H:8]([C@H:10]1[C:25](=[O:26])[N:12]2[C:13]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])=[C:14]([CH2:17]O)[C@H:15]([CH3:16])[C@H:11]12)[CH3:9])=[O:6])[CH:2]=[CH2:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:46][N:47]1[C:51]2=[C:52]3[C:57](=[CH:58][CH:59]=[C:50]2[NH:49][S:48]1(=[O:70])=[O:69])[CH:56]=[CH:55][C:54]([CH2:60][O:61][Si:62]([CH2:67][CH3:68])([CH2:65][CH3:66])[CH2:63][CH3:64])=[CH:53]3.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.C(Cl)(Cl)Cl>[CH2:1]([O:4][C:5]([O:7][C@@H:8]([C@H:10]1[C:25](=[O:26])[N:12]2[C:13]([C:19]([O:21][CH2:22][CH:23]=[CH2:24])=[O:20])=[C:14]([CH2:17][N:49]3[C:50]4=[CH:59][CH:58]=[C:57]5[C:52]([CH:53]=[C:54]([CH2:60][O:61][Si:62]([CH2:67][CH3:68])([CH2:63][CH3:64])[CH2:65][CH3:66])[CH:55]=[CH:56]5)=[C:51]4[N:47]([CH3:46])[S:48]3(=[O:70])=[O:69])[C@H:15]([CH3:16])[C@H:11]12)[CH3:9])=[O:6])[CH:2]=[CH2:3]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 11046746allyl (1S,5R,6S)-2-(hydroxymethyl)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methylcarbapen-2-em-3-carboxylateHCID 155380561-Methyl-8-triethylsilanyloxymethyl-1,3-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalene 2,2-dioxide

Product 1

HCID 15538057allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[alpha]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-2-hydroxymethyl-1-methyl-carbapen-2-em-3-carboxylate (365 mg, 1.0 mmol), triphenylphosphine (315 mg, 1.2 mmol), and 1-methyl-8-triethylsilanyloxymethyl-1,3-dihydro-2-thia-1,3-diaza-cyclopenta[α]naphthalene 2,2-dioxide (416 mg, 1.1 mmol) in anhydrous tetrahydrofuran (7 mL) is cooled in an ice-bath and stirred under a nitrogen atmosphere while diisopropyl azodicarboxylate (0.24 mL, 1.2 mmol) is added dropwise over a few minutes. The resulting solution is stirred in the cold for 30 minutes, then diluted with chloroform, washed with 5% aqueous sodium bicarbonate and brine, dried over sodium sulfate, filtered and evaporated under vacuum. The residue is purified by silica gel flash chromatography, eluting with hexane-ethyl acetate, to afford allyl (1S,5R,6S)-6-[1(R)-allyloxycarbonyloxy-ethyl]-1-methyl-2-(1-methyl-2,2-dioxo-8-triethylsilanyloxymethyl-1,2-dihydro-2-thia-1,3-diaza-cyclopenta[α]naphthalen-3-ylmethyl)-carbapen-2-em-3-carboxylate.

Workup

  1. additionis added dropwise over a few minutes
  2. washwashed with 5% aqueous sodium bicarbonate and brine
  3. dry with materialdried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated under vacuum
  6. customThe residue is purified by silica gel flash chromatography
  7. washeluting with hexane-ethyl acetate

Sources & evidence

ORD record
ord-ff41e205f0f3407dacd8d82812068230
Source dataset
uspto-grants-2001_09
Patent number
US06291448B1

Reaction notes

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