Dichloromethane → tert-butyl (1S)-1-[4-(2-tert-butyl-1,1-dioxido-3-oxo-2,3-dihydroisothiazol-5-yl)benzyl]-2-hydroxyethylcarbamate

HRID 724600Notes

Reaction equation

HRID 724600 reaction equation
[OH:1][CH2:2][C@H:3]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:4][C:5]1[CH:10]=[CH:9][C:8](B2OC(C)(C)C(C)(C)O2)=[CH:7][CH:6]=1.[C:28]([N:32]1[C:36](=[O:37])[CH:35]=[C:34](Cl)[S:33]1(=[O:40])=[O:39])([CH3:31])([CH3:30])[CH3:29].C(=O)([O-])[O-].[K+].[K+].ClCCl>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[C:28]([N:32]1[C:36](=[O:37])[CH:35]=[C:34]([C:8]2[CH:7]=[CH:6][C:5]([CH2:4][C@H:3]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:24])([CH3:25])[CH3:26])[CH2:2][OH:1])=[CH:10][CH:9]=2)[S:33]1(=[O:39])=[O:40])([CH3:31])([CH3:29])[CH3:30]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 218786382-Tert-butyl-5-chloro-2,3-dihydro-1lambda6,2-thiazole-1,1,3-trioneHCID 86602075tert-butyl {(1R)-2-hydroxy-1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl]ethyl}carbamate

Product 1

HCID 58746779tert-butyl (1S)-1-[4-(2-tert-butyl-1,1-dioxido-3-oxo-2,3-dihydroisothiazol-5-yl)benzyl]-2-hydroxyethylcarbamateYield 163.5%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

Combined 34-A (6.1 g, 61 mmol), 9-A (3.55 g, 15.9 mmol), potassium carbonate (10.0 g, 72.4 mmol), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex with dichloromethane (1:1) (2.50 g, 3.06 mmol) in 200 mL dioxane. The reaction was degassed and heated at 90° C. for 48 hours. The crude was extracted with ethyl acetate, washed with water and brine. The combined organic extracts were dried over Na2SO4, filtered and evaporated to give 11.4 g of a dark glass. The crude was chromatographed on a silica column to afford a dark semi-solid (3.3 g, 90%). 1H NMR (500 MHz, CDCl3): δ 7.72 (d, J=8.8 Hz, 2H), 7.38 (d, J=8.8 Hz, 2H), 6.62 (s, 1H), 4.77 (br s, 1H), 3.89 (br s, 1H), 3.69 (m, 1H), 3.58 (m, 1H), 2.93 (d, J=7.2 Hz, 2H) 1.43 (s, 9H), 1.39 (s, 9H).

Workup

  1. customThe reaction was degassed
  2. extractionThe crude was extracted with ethyl acetate
  3. washwashed with water and brine
  4. dry with materialThe combined organic extracts were dried over Na2SO4
  5. filtrationfiltered
  6. customevaporated

Sources & evidence

ORD record
ord-ac51c16b69c94d40bc327f6d397a29e2
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Reaction notes

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