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p-Toluenesulfonic acid → HCID 11174412, compound

HRID 459190
Notes
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Reaction equation

HRID 459190 reaction equation
C(OC1C=CC(C[C@H](O)C(O)=O)=CC=1)C1C=CC=CC=1.[CH2:21]([O:28][C:29]1[CH:43]=[CH:42][C:32]([CH2:33][C@@H:34]2[O:38][C:37]([CH3:40])([CH3:39])[O:36][C:35]2=[O:41])=[CH:31][CH:30]=1)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.COC(OC)(C)C.CC1C=CC(S(O)(=O)=O)=CC=1>C(Cl)(Cl)Cl.O>[CH2:21]([O:28][C:29]1[CH:43]=[CH:42][C:32]([CH2:33][C@@H:34]2[O:38][C:37]([CH3:40])([CH3:39])[O:36][C:35]2=[O:41])=[CH:31][CH:30]=1)[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 64952,2-DimethoxypropaneHCID 86596245(S)-5-(4-benzyloxy-benzyl)-2,2-dimethyl-[1,3]dioxolan-4-one (S)-3-(4-benzyloxy-phenyl)-2-hydroxy-propionic acid

Product 1

HCID 11174412HCID 11174412, compoundYield 88%

Reagents, catalysts & solvents 2

HCID 962Water
Solvent
HCID 6212ChloroformSolvent

Procedure

A solution containing (S)-5-(4-benzyloxy-benzyl)-2,2-dimethyl-[1,3]dioxolan-4-one (S)-3-(4-benzyloxy-phenyl)-2-hydroxy-propionic acid (2.0 g, 7.34 mmol), 2,2-dimethoxypropane (18.63 g, 0.179 mol) and pyrididium p-toluene sulfonate (0.92 g, 3.66 mmol) in chloroform (80 mL) was heated to reflux for 40 minutes under N2. The reaction was cooled, diluted with water and extracted with CH2Cl2. The organic layer was dried (Na2SO4) and the solvent was removed in vacuo to give crude product which was purified by a flash chromatography using 10:1 hexanes:acetone to afford about 2.01 g (88%) of (S)-5-(4-benzyloxy-benzyl)-2,2-dimethyl-[1,3]dioxolan-4-one. 1H NMR (400 MHz, CDCl3) δ 7.43–7.29 (m, 5H), 7.17 (d, 2H, J=8.80 Hz), 6.91 (d, 2H, J=8.80 Hz), 5.04 (s, 2H), 4.61 (dd, 1H, J=6.36 Hz, J=4.40 Hz), 3.12 (dd, 1H, J=14.67 Hz, J=4.40 Hz), 2.99 (dd, 1H, J=14.67 Hz, J=6.36 Hz), 1.49 (s, 3H), 1.36 (s, 3H). MS (ES+) m/z exact mass calculated for C19H20O4 (M+NH4) 330. Found m/z 330. Step 2: (S)-3-(4-benzyloxy-phenyl)-2-isopropoxy-propionic acid A −78° C. solution of (S)-5-(4-benzyloxy-benzyl)-2,2-dimethyl-[1,3]dioxolan-4-one (0.20 g, 0.64 mmol) and triethylsilane (0.223 g, 1.92 mmol) in CH2Cl2 (8 mL) was treated dropwise with a 1 molar solution of TiCl4 in CH2Cl2 (0.64 mL, 0.64 mmol) under N2. The solution was stirred at −78° C. for 15 minutes and then quenched with water. The mixture was extracted with EtOAc, and the organic layer was dried (Na2SO2). The organic layer was filtered, and the solvent was removed in vacuo to give crude product which was purified by a flash chromatography using 5:1 hexanes:acetone to afford 0.171 g (85%) (S)-3-(4-benzyloxy-phenyl)-2-isopropoxy-propionic acid. 1H NMR (400 MHz, DMSO-d6) δ 12.50 (bs, 1H), 7.42–7.27 (m, 5H), 7.12 (d, 2H, J=8.80 Hz), 6.88 (d, 2H, J=8.80 Hz), 5.02 (s, 2H), 3.96 (dd, 1H, J=7.83 Hz, J=4.89 Hz), 3.47 (hp, 1H, J=5.87 Hz), 2.83 (dd, 1H, J=13.69 Hz, J=4.89 Hz), 2.71 (dd, 1H, J=13.69 Hz, J=8.31 Hz), 1.02 (d, 2H, J=5.87 Hz), 0.86 (d, 2H, J=5.87 Hz). IR (KBr) 3012, 2977, 2931, 1767, 1722, 1610, 1511, 1380, 1240, 1116, 1020. HRMS (TOF ES−) m/z exact mass calculated for C19H21O4 (M−1) 13.1440. Found m/z 313.1434.

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 40 minutes under N2
  3. temperatureThe reaction was cooled
  4. extractionextracted with CH2Cl2
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. customthe solvent was removed in vacuo
  7. customto give crude product which
  8. customwas purified by a flash chromatography

Sources & evidence

ORD record
ord-d425b48a5cdf4cffa3586167ef2f571b
Source dataset
uspto-grants-2007_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07192982B2

Reaction notes

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