Tributylstannane → HCID 86748804, compound

HRID 1648116Notes

Reaction equation

HRID 1648116 reaction equation
C(OC([NH:7][CH:8]1[CH:12]([O:13]CC2C=CC=CC=2)[O:11][C:10](=[O:21])[CH2:9]1)=O)C=C.C(O[C:27]([NH:29][C@H:30]([C:34]([NH:36][C@H:37]([C:39]([OH:41])=O)[CH3:38])=[O:35])[CH:31]([CH3:33])[CH3:32])=[O:28])(C)(C)C.[CH2:42]([SnH](CCCC)CCCC)[CH2:43]CC.O[C:56]1[C:64]2N=NN[C:60]=2[CH:59]=[CH:58][CH:57]=1.C(N=C=NCCCN(C)C)C>ClCCl.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CN(C)C=O>[C:56]1([CH2:42][CH2:43][C:27]([NH:29][C@H:30]([C:34]([NH:36][C@H:37]([C:39]([NH:7][CH:8]([CH:12]=[O:13])[CH2:9][C:10]([OH:21])=[O:11])=[O:41])[CH3:38])=[O:35])[CH:31]([CH3:32])[CH3:33])=[O:28])[CH:64]=[CH:60][CH:59]=[CH:58][CH:57]=1

Participants

10

Reactant 5

HCID 5948Tributylstannane2×HCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 14657712N-(tert-Butoxycarbonyl)-L-valyl-L-alanineHCID 22321532(2-Benzyloxy-5-oxo-tetrahydro-furan-3-yl)-carbamic acid allyl esterHCID 178418300HCID 178418300, compound

Product 1

HCID 86748804HCID 86748804, compoundYield 100.6%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of N-allyloxycarbonyl-4-amino-5-benzyloxy-2-oxotetrahydrofuran (407.6 mg, 1.399 mmol) and tert-butoxycarbonyl-valinyl-alanine (807 mg, 2.8 mmol) in 10 mL of dichloromethane was added ~20 mg of (PPh3)2PdCl2 followed by tri-n-butyltin hydride (415 μL, 1.54 mmol) dropwise over two minutes. An additional 100 μl of tri-n-butyltin hydride was added dropwise until the color of the reaction mixture had turned dark orange. Dimethylformamide (5 mL0 was added followed by hydroxybenzotriazole (567 mg, 4.2 mmol). The mixture was cooled to 0° C. and ethyl dimethylaminopropyl carbodiimide (295 mg, 1.54 mmol) was added. After 16 hours at ambient temperature, the mixture was diluted with ethyl acetate and washed three times with dilute hydrochloric acid, and three times with dilute sodium bicarbonate. The mixture was dried over sodium sulfate, filtered, and concentrated. The residue was purified by MPLC on silica-gel (22×300 mm column, 50% ethyl acetate in hexane as eluent) to afford 590.4 mg (91%) of the title compound as a mixture of two diastereomers: 1H NMR (400 MHz, CD3OD) δ7.4-7.05 (m, 5H, Ar--H), 5.63 (d, 0.5H, CHOBn), 5.45 (d, 0.5H, CHOBn), 4.9-4.6 (m, 3H, CH2Ph, CHN), 4.4-4.2 (m, 2H, CHN), 3.83 (m, 1H, CHN), 3.03 (dd, 0.5H, CHHCO2), 2.77 (dd, 0.5H, CHHCO2), 2.61 (dd, 0.5H, CHHCO2), 2.47 (dd, 0.5H, CHHCO2), 2.01 (m, 1H, CH(CH3)2), 1.43 (s, 9H, C(CH3)3), 1.33 (d, 1.5H, CHCH3), 1.27 (d, 1.5H, CHCH3), 0.9 (m, 6H, CH(CH3)2). ##STR34## N-(3-(4-Hydroxyphenyl)-propionyl-valinyl-alaninyl)-4-amino-5-benzyloxy-2-oxotetrahydrofuran

Workup

  1. washwashed three times with dilute hydrochloric acid, and three times with dilute sodium bicarbonate
  2. dry with materialThe mixture was dried over sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by MPLC on silica-gel (22×300 mm column, 50% ethyl acetate in hexane as eluent)

Sources & evidence

ORD record
ord-2d3b77f5dd6046f0952654fab492dc14
Source dataset
uspto-grants-1995_07
Patent number
US05434248

Reaction notes

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