Dimethyl Sulfoxide → Ethyl 2-(tert-butoxycarbonylamino)-2-formyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate

HRID 579516

反応式

HRID 579516 の反応式
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([O:15][C:16]([NH:18][C:19]([CH2:38][OH:39])([CH2:25][CH2:26][CH2:27][CH2:28][B:29]1[O:33][C:32]([CH3:35])([CH3:34])[C:31]([CH3:37])([CH3:36])[O:30]1)[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[O:17])([CH3:14])([CH3:13])[CH3:12].C(N(CC)CC)C>ClCCl>[C:11]([O:15][C:16]([NH:18][C:19]([CH:38]=[O:39])([CH2:25][CH2:26][CH2:27][CH2:28][B:29]1[O:30][C:31]([CH3:37])([CH3:36])[C:32]([CH3:35])([CH3:34])[O:33]1)[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[O:17])([CH3:14])([CH3:12])[CH3:13]

参加物

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 66833197Ethyl 2-(tert-butoxycarbonylamino)-2-(hydroxymethyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate

生成物 1

HCID 86663719Ethyl 2-(tert-butoxycarbonylamino)-2-formyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate収率 57%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒3 回

実験手順

While under an argon atmosphere, a solution of oxalyl chloride (1.46 g, 0.88 mL, 11.6 mmol) in dichloromethane (15 mL) was cooled to −78° C. and treated with dimethyl sulfoxide (1.8 g, 1.64 mL, 23.2 mmol) and stirred for 10 minutes. To this mixture ethyl 2-(tert-butoxycarbonylamino)-2-(hydroxymethyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate (2.4 g, 5.78 mmol) in anhydrous dichloromethane (15 mL) was added and the mixture was stirred for 30 minutes. The reaction mixture was quenched by adding triethylamine (3.5 g, 4.8 mL, 34.7 mmol) at −78° C. and slowly warming the reaction mixture to room temperature. The mixture was diluted with dichloromethane (25 mL) and washed successively with water (2×25 mL) and saturated aqueous sodium chloride (25 mL). Organic layer was dried over magnesium sulfate, filtered and evaporated to dryness. The resulting residue was purified using a combiflash system (40 g column, eluted with 20-40% ethyl acetate in heptanes) to give ethyl 2-(tert-butoxycarbonylamino)-2-formyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate (1.35 g, 57%). 1HNMR (CDCl3) δ 9.58 (s, 1H), 5.64 (bs, 1H), 4.25 (m, 2H), 2.13 (m, 2H), 1.45 (m, 9H), 1.28 (m, 4H), 1.24 (s, 12H), 0.88 (t, J=6.4 Hz, 3H), 0.77 (t, J=7.9 Hz, 2H). MS found for C20H36BNO7 m/z[436(M+Na)].

後処理

  1. stirringthe mixture was stirred for 30 minutes
  2. customThe reaction mixture was quenched
  3. washwashed successively with water (2×25 mL) and saturated aqueous sodium chloride (25 mL)
  4. dry with materialOrganic layer was dried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe resulting residue was purified
  8. washa combiflash system (40 g column, eluted with 20-40% ethyl acetate in heptanes)

出典と根拠

ORDレコード
ord-252601c45157424bb74481dfac5052a4
出典データセット
uspto-grants-2015_05
特許番号
US09040703B2

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