二氯甲烷 → (1S,2S)-1-acetamido-N-tert-butyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)cyclopentanecarboxamide

HRID 61347

反应方程式

HRID 61347 反应方程式
[C:1]([NH:4][C@@:5]1([C:13]([NH:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8][CH2:7][C@@H:6]1[CH2:10][CH:11]=[CH2:12])(=[O:3])[CH3:2].C(Cl)Cl.[CH3:23][C:24]1([CH3:31])[C:28]([CH3:30])([CH3:29])[O:27][BH:26][O:25]1>C1C=CC(P(C2C=CC=CC=2)CCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:1]([NH:4][C@@:5]1([C:13]([NH:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8][CH2:7][C@@H:6]1[CH2:10][CH2:11][CH2:12][B:26]1[O:27][C:28]([CH3:30])([CH3:29])[C:24]([CH3:31])([CH3:23])[O:25]1)(=[O:3])[CH3:2]

参与物

6

反应物 3

HCID 6344二氯甲烷HCID 2734768频那醇硼烷HCID 69669622(1S,2R)-1-acetamido-2-allyl-N-tert-butylcyclopentanecarboxamide

产物 1

HCID 69669489(1S,2S)-1-acetamido-N-tert-butyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl)cyclopentanecarboxamide收率 78.3%

试剂、催化剂与溶剂 2

HCID 742671,2-双(二苯基膦)乙烷催化剂HCID 962聚[6-[4-(4-氰基苯基)苯氧基]己基甲基丙烯酸酯]溶剂

实验过程

A stirred solution of (1S,2R)-1-acetamido-2-allyl-N-tert-butylcyclopentanecarboxamide (0.599 g, 2.25 mmol) in an anhydrous methylene chloride (9 mL) under nitrogen was treated with Ir2Cl2(COD)2 (45 mg, 0.07 mmol) and DiPhos (54 mg, 0.136 mmol) and stirred at room temperature for 30 min. 4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (0.65 mL, 4.48 mmol) was added dropwise and the solution stirred at room temperature for 20 h. The reaction mixture was poured into water (20 mL) and extracted with ethyl acetate (40 mL, then 2×15 mL), and the combined organic solution was washed with saturate aqueous sodium chloride (30 mL), dried over MgSO4, and concentrated. The residue was dissolved in minimal dichloromethane and purified by flash column chromatography (silica gel, 40-50% ethyl acetate in heptane) to afford (1S,2S)-1-acetamido-N-tert-butyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl) cyclopentanecarboxamide (0.695 g, 78%) as a white solid. 1H NMR (CDCl3, 300 MHz) δ 6.72 (br s, NH, 1 H), 5.68 (br s, NH, 1 H), 2.46-2.29 (m, 2 H), 2.10-2.19 (m, 1 H), 2.02 (s, 3 H), 2.00-1.88 (m, 1 H), 1.75-1.60 (m, 3 H), 1.52-1.38 (4 H), 1.32 (s, 9 H), 1.31 (s, 12 H), 0.81-0.70 (m, 2 H); MS (+CI): m/z for C21H39BN2O4: expected 394.3; found 395.2 (M+H)+.

后处理

  1. stirringthe solution stirred at room temperature for 20 h
  2. extractionextracted with ethyl acetate (40 mL
  3. wash2×15 mL), and the combined organic solution was washed with saturate aqueous sodium chloride (30 mL)
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in minimal dichloromethane
  7. custompurified by flash column chromatography (silica gel, 40-50% ethyl acetate in heptane)

来源与证据

ORD记录
ord-46d8db09e1b0440c98cacf2ddefd7b4b
来源数据集
uspto-grants-2016_09
专利号
US09440995B2

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