(Dimethyl sulfide)trihydroboron → Ethyl 5-oxa-6-azaspiro[3.4]octane-7-carboxylate

HRID 417728ノート

反応式

HRID 417728 の反応式
[CH2:1]([O:3][C:4]([C:6]1[CH2:13][C:9]2([CH2:12][CH2:11][CH2:10]2)[O:8][N:7]=1)=[O:5])[CH3:2].CSC.B>O1CCCC1>[CH2:1]([O:3][C:4]([CH:6]1[CH2:13][C:9]2([CH2:10][CH2:11][CH2:12]2)[O:8][NH:7]1)=[O:5])[CH3:2]

参加物

4

反応物 2

HCID 12423031(Dimethyl sulfide)trihydroboronHCID 59611573Ethyl 5-oxa-6-azaspiro[3.4]oct-6-ene-7-carboxylate

生成物 1

HCID 59611538Ethyl 5-oxa-6-azaspiro[3.4]octane-7-carboxylate収率 29%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

To a solution of crude 5-oxa-6-aza-spiro[3.4]oct-6-ene-7-carboxylic acid ethyl ester (7.5 g, <40.9 mmol) in tetrahydrofuran (270 mL) at 0° C. was slowly added a solution of borane-dimethyl sulfide complex (10 M in THF, 16.4 mL, 164 mmol). The reaction was allowed to warm to room temperature overnight then recooled to 0° C., and quenched by the careful addition of water. The mixture was diluted with ethyl acetate, washed with water and brine, dried (MgSO4), and concentrated to yield a large amount of white solids. These solids were thoroughly triturated three times with dichloromethane (150 mL). The combined dichloromethane washings were concentrated and the resulting oil was purified by flash chromatography to yield 5-oxa-6-aza-spiro[3.4]octane-7-carboxylic acid ethyl ester (1.08 g, 29% over 2 steps). 1H-NMR: 400 MHz, (CDCl3) δ: 8.01-7.95 (br, 1H), 4.39-4.28 (m, 2H), 4.18-4.10 (m, 1H), 2.80-2.75 (m, 1H), 2.62-2.49 (m, 2H), 2.37-2.29 (m, 1H), 2.25-2.17 (m, 1H), 2.13-1.95 (m, 1H), 1.88-1.79 (m, 1H), 1.68-1.56 (m, 1H), 1.34 (t, J=7.1 Hz, 3H) ppm.

後処理

  1. customthen recooled to 0° C.
  2. customquenched by the careful addition of water
  3. additionThe mixture was diluted with ethyl acetate
  4. washwashed with water and brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customto yield a large amount of white solids
  8. customThese solids were thoroughly triturated three times with dichloromethane (150 mL)
  9. concentrationThe combined dichloromethane washings were concentrated
  10. customthe resulting oil was purified by flash chromatography

出典と根拠

ORDレコード
ord-1148a1d2cd2548f7a297f340e9ce9874
出典データセット
uspto-grants-2012_01
特許番号
US08088368B2

反応ノート

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