ChemicalBook CAS DataBase List (S)-tert-butyl 2-(4-(4-chlorophenyl)-2,3,9-triMethyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepin-6-yl)acetate

(S)-tert-butyl 2-(4-(4-chlorophenyl)-2,3,9-triMethyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepin-6-yl)acetate synthesis

9synthesis methods

Product Name:(S)-tert-butyl 2-(4-(4-chlorophenyl)-2,3,9-triMethyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepin-6-yl)acetate
CAS Number:1268524-70-4
Molecular formula:C23H25ClN4O2S
Molecular Weight:456.99

1H-Thieno[2,3-e]-1,4-diazepine-3-acetic acid, 5-(4-chlorophenyl)-2,3-dihydro-6,7-diMethyl-2-oxo-, 1,1-diMethylethyl ester, (3S)-

1268524-67-9
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1068-57-1 Synthesis

1068-57-1
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(S)-tert-butyl 2-(4-(4-chlorophenyl)-2,3,9-triMethyl-6H-thieno[3,2-f][1,2,4]triazolo[4,3-a][1,4]diazepin-6-yl)acetate

1268524-70-4
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$39.00/1mg

Yield:1268524-70-4 92%

Reaction Conditions:

Stage #1:tert-butyl (S)-2-(5-(4-chlorophenyl)-6,7-dimethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-3-yl)acetate with potassium tert-butylate in tetrahydrofuran at -78 - 23; for 0.5 h;
Stage #2: with diethyl chlorophosphate in tetrahydrofuran at -10; for 0.75 h;
Stage #3:acetic acid hydrazide in tetrahydrofuran;butan-1-ol at 23 - 90; for 2 h;

Steps:

Potassium tert-butoxide (1.0 M solution in THF, 0.3 ml, 0.30 mmol, 1.10 equiv) was added to a solution of S5 (114 mg, 0.27 mmol, 1 equiv) in THF (1.8 ml, 0.15 M) at -78 °C. The reaction mixture was warmed to -10 °C, and stirred at 23 °C for 30 min. The reaction mixture was cooled to -78 °C. Diethyl chlorophosphate (0.047 ml, 0.32 mmol, 1.20 equiv) was added to reaction mixture 22. The resulting mixture was warmed to -10 °C over 45 min. Acetic hydrazide (30 mg, 0.40 mmol, 1.50 equiv) was added to reaction mixture. The reaction mixture was stirred at 23 °C. After 1 h, 1-butanol (2.25 ml) was added to reaction mixture, which was heated to 90 °C. After 1 h, all solvents were removed under reduce pressure. The residue was purified with flash column chromatography (Combiflash system, 4 g silica gel, gradient 0 to 100 % ethyl acetate-hexanes) to afford (+)-JQl (114 mg, 92 %) as white solid with 90 % enantiomeric purity (determined with Berger Supercritical Fluid Chromatography (SFC) using AS-H column, 85 % hexanes- methanol, 210 nm, t_R (R- enantiomer) = 1.59 min, t_R (S-enantiomer) = 3.67 min). The product was further purified by chiral preparative HPLC (Agilent High Pressure Liquid Chromatography using an OD-H column) to provide the S-enantiomer in greater than 99 % ee.1H NMR (600 MHz, CDC1₃, 25 °C) δ 7.39 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H),4.54 (t, J = 6.6 MHz, 1H), 3.54-3.52 (m, 2H), 2.66 (s, 3H), 2.39 (s, 3H), 1.67 (s, 3H), 1.48 (s, 9H).¹³C NMR (150 MHz, CDC1₃, 25 °C) δ 171.0, 163.8, 155.7, 150.0, 136.9, 131.1, 130.9, 130.6, 130.3, 128.9, 81.2, 54.1, 38.1, 28.4, 14.6, 13.5, 12.1.HRMS(ESI) calc'd for C₂iH₂₄ClN₂0₃S [M+H]⁺: 457.1460, found 457.1451 m/z.TLC (EtOAc), Rf: 0.32 (UV)[a]²²_D = + 75 (c 0.5, CHCl₃)