Tetrahydrofuran → (S)-tert-butyl 3-bromo-7-((3-methyloxetan-3-yl)ethynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-thiazole]-2'-ylcarbamate

HRID 335941

反応式

HRID 335941 の反応式
[Br:1][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](I)[CH:13]=3)[O:8][C:5]2=[N:6][CH:7]=1.O.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.C1COCC1.C[Si](C)(C)[C:55]#[C:56][C:57]1([CH3:61])[CH2:60][O:59][CH2:58]1>CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[Br:1][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:55]#[C:56][C:57]4([CH3:61])[CH2:60][O:59][CH2:58]4)[CH:13]=3)[O:8][C:5]2=[N:6][CH:7]=1

参加物

8

反応物 4

HCID 8028TetrahydrofuranHCID 162116731-Butanaminium, N,N,N-tributyl-, fluoride, hydrateHCID 58547788Trimethyl((3-methyloxetan-3-yl)ethynyl)silaneHCID 67382944(S)-tert-butyl 3-bromo-7-iodo-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-thiazole]-2'-ylcarbamate

生成物 1

HCID 67437931(S)-tert-butyl 3-bromo-7-((3-methyloxetan-3-yl)ethynyl)-5'H-spiro[chromeno[2,3-b]pyridine-5,4'-thiazole]-2'-ylcarbamate収率 89%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418397HCID 178418397、化合物触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

A vial was charged with (S)-tert-butyl 3-bromo-7-iodo-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-thiazole]-2′-ylcarbamate (0.194 g, 0.338 mmol), tetrakis(triphenylphosphine)palladium (0.039 g, 0.034 mmol), tetrabutylammonium fluoride hydrate (0.41 g, 1.689 mmol), and copper(I) iodide (6.43 mg, 0.034 mmol). Added THF (1.7 mL) followed by trimethyl((3-methyloxetan-3-yl)ethynyl)silane (0.10 mL, 0.51 mmol). The reaction was stirred at 60° C. for 30 min, then 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 column chromatography on silica gel (0-50% EtOAc:Hex) to afford (S)-tert-butyl 3-bromo-7-((3-methyloxetan-3-yl)ethynyl)-5′H-spiro[chromeno[2,3-b]pyridine-5,4′-thiazole]-2′-ylcarbamate (0.163 g, 0.30 mmol, 89% yield) as a yellow solid.

後処理

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

出典と根拠

ORDレコード
ord-f8a6e25be6d040dba6866a60267af512
出典データセット
uspto-grants-2014_11
特許番号
US08883782B2

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