Dichloromethane → (R)-Phenyl(p-tolyl)methanol

1.0 mL (12 mmol) of anhydrous 1,4-dioxane was added to 0.375 mL (0.375 mmol) of an anhydrous THF solution (1.00 mol/L) of commercial phenylmagnesium bromide, and the contents were stirred for 10 minutes, and then 0.402 mL (0.325 mmol) of an anhydrous dichloromethane solution (0.80 mol/L) of chloro-tri-iso-propoxy titanium prepared in Preparation Example 1 was added thereto, and further stirred for 10 minutes. 0.25 mL (0.0125 mmol) of an anhydrous dichloromethane solution (0.050 mol/L) of (R)—H8-BINOL was added thereto and stirred at room temperature for 30 minutes. The thus-obtained solution containing a white precipitate was added dropwise to 30 mg (0.25 mmol) of a dichloromethane solution (0.5 mL) of p-tolualdehyde using a syringe over a period of 10 minutes, and stirred at room temperature for 1 hour for the reaction. Thereafter, an operation was carried out in the same manner as in Example 1 to obtain (R)-4-methylbenzhydrol. The conversion rate of the raw material was 80%, while the enantiomeric excess of the product was 94% ee. The amount of dioxane used during the reaction was 32 equivalents (64 equivalents in terms of the ether oxygen equivalent) relative to magnesium.

1. additionwas added
2. stirringfurther stirred for 10 minutes
3. stirringstirred at room temperature for 30 minutes
4. additionThe thus-obtained solution containing a white precipitate
5. stirringstirred at room temperature for 1 hour for the reaction

ORD record

ord-a0d6d90fcf894a76bb60c844fd64a734

Source dataset

uspto-grants-2013_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08563786B2