Réaction #167939

Équation de réaction

KOH

3-hydroxy-4-methylphenyl boronic acid

3-((phenylsulfonyl)methylene)oxetane

KOH

→

2-methyl-5-(3-((phenylsulfonyl)methyl)oxetan-3-yl)phenol

Solvants

dioxane

dioxane

Conditions de réaction

Traitement

1. 1
   workup.WAITAfter 1 h
2. 2
   workup.WAITAfter another 10 min
3. 3
   workup.STIRRINGThe resulting mixture was stirred at room temperature overnight
4. 4
   Autrepartitioned between Et2O and aqueous NH4Cl
5. 5
   ExtractionThe aqueous layer was extracted with Et2O (3×)
6. 6
   Extraction(During extractions
7. 7
   SéchageThe combined organic layers were dried (Na2SO4)
8. 8
   Filtrationfiltered
9. 9
   Concentrationconcentrated
10. 10
    AutreThe dark orange residue was purified by silica gel chromatography (30-100% EtOAc/heptane)

Mode opératoire

A solution of KOH (1.5 M in water, 14.2 mL, 21.3 mmol) was added to a solution of [Rh(cod)C1]2 (0.525 g, 1.07 mmol) in dioxane (60 mL). The resulting yellow solution was stirred for 1 min. Then, 3-hydroxy-4-methylphenyl boronic acid (6.48 g, 42.6 mmol) and a solution of 3-((phenylsulfonyl)methylene)oxetane (4.48 g, 21.3 mmol) in dioxane (40 mL) were added in that order. After 1 h, a solution of KOH (1.5 M in water, 14.2 mL, 21.3 mmol) was added. After another 10 min, [Rh(cod)Cl]2 (0.525 g, 1.07 mmol) was added. The resulting mixture was stirred at room temperature overnight, and then partitioned between Et2O and aqueous NH4Cl. The aqueous layer was extracted with Et2O (3×). (During extractions, some solids crashed out in the organic layer, but went back into solution over time). The combined organic layers were dried (Na2SO4), filtered, and concentrated. The dark orange residue was purified by silica gel chromatography (30-100% EtOAc/heptane) to provide 2-methyl-5-(3-((phenylsulfonyl)methyl)oxetan-3-yl)phenol. 1H NMR (400 MHz, CD2Cl2) δ ppm 7.52-7.63 (m, 3 H) 7.41 (t, J=7.71 Hz, 2 H) 6.99 (d, J=7.83 Hz, 1 H) 6.57 (dd, J=7.83, 1.77 Hz, 1 H) 6.50 (d, J=2.02 Hz, 1 H) 4.99 (d, J=6.57 Hz, 2 H) 4.91 (d, J=6.57 Hz, 2 H) 4.03 (s, 2 H) 2.20 (s, 3 H)

Source