Dimethylformamide → HCID 67383170, compound

HRID 335847

Reaction equation

HRID 335847 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C@:15]3([CH2:19][S:18][C:17]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[N:16]3)[C:14]3[C:9](=[CH:10][CH:11]=[C:12]([C:28]4[C:29]([F:34])=[N:30][CH:31]=[CH:32][CH:33]=4)[CH:13]=3)[O:8][C:5]2=[N:6][CH:7]=1.CN(C=O)C.C[Si](C)(C)[C:42]#[C:43][C:44]1([CH3:48])[CH2:47][O:46][CH2:45]1>CCOC(C)=O.[Cu]I.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.CC(P(C(C)(C)C)C1C=CC(N(C)C)=CC=1)(C)C.Cl[Pd]Cl>[F:34][C:29]1[C:28]([C:12]2[CH:13]=[C:14]3[C@@:15]4([CH2:19][S:18][C:17]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:25])([CH3:26])[CH3:24])=[N:16]4)[C:4]4[C:5](=[N:6][CH:7]=[C:2]([C:42]#[C:43][C:44]5([CH3:48])[CH2:47][O:46][CH2:45]5)[CH:3]=4)[O:8][C:9]3=[CH:10][CH:11]=2)=[CH:33][CH:32]=[CH:31][N:30]=1

Participants

7

Reactant 3

HCID 6228DimethylformamideHCID 58547788Trimethyl((3-methyloxetan-3-yl)ethynyl)silaneHCID 67382906(5)-tert-butyl 3-bromo-7-(2-fluoropyridin-3-yl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-thiazole]-2'-ylcarbamate

Product 1

HCID 67383170HCID 67383170, compound

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 11714597Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II)CatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A vial was charged with (5)-tert-butyl 3-bromo-7-(2-fluoropyridin-3-yl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-thiazole]-2′-ylcarbamate (0.181 g, 0.333 mmol), copper(i) iodide (0.013 g, 0.067 mmol), and bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) (0.024 g, 0.033 mmol). The vial was flushed with Ar (g), then DMF (1.665 mL), DIPA (0.712 mL, 5.00 mmol), and trimethyl((3-methyloxetan-3-yl)ethynyl)silane (0.201 mL, 0.999 mmol) were added in sequence. The reaction was heated to 90° C. and stirred for three hours. The reaction was diluted with EtOAc and washed with water. The aqueous layer was extracted with EtOAc, and the combined organic layers were dried with sodium sulfate, filtered, and concentrated. The material was purified via silica gel chromatography (gradient elution 0-50% EtOAc:Hex) to afford (S)-tert-butyl 7-(2-fluoropyridin-3-yl)-3-((3-methyloxetan-3-yl)ethynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-thiazole]-2′-ylcarbamate as a yellow solid. MS m/z=559.2. Calc'd for C30H27FN4O4S: 558.62.

Workup

  1. customThe vial was flushed with Ar (g)
  2. washwashed with water
  3. extractionThe aqueous layer was extracted with EtOAc
  4. dry with materialthe combined organic layers were dried with sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe material was purified via silica gel chromatography (gradient elution 0-50% EtOAc:Hex)

Sources & evidence

ORD record
ord-d3a255be5977481281c5e05204c7f928
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Linked notes

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