Carbon Dioxide → methyl (S)-2-hydroxy-3-(1-cyclohexenyl)propanoate

Into a 25-ml flask was placed 0.5 g of a powder of Molecular Sieves® 4A (manufactured by Aldrich Corp.), and the air in the flask was thoroughly displaced by argon. Then, 5 ml of methylene chloride was added thereto, and 0.16 ml (0.05 mmole) of the diisopropoxydibromotitanium solution in toluene as prepared above and 14.3 mg (0.05 mmole) of (R)-binaphthol were further added. The mixture was stirred at room temperature for 1 hour to prepare an (R)-binaphtholdibromotitanium complex. This solution was cooled to -30° C. in a bath of dry ice and acetone, and subsequently 96 mg (1 mmole) of methylenecyclohexane (manufactured by Aldrich Corp.) and 88 mg (1 mmole) of methyl glyoxylate were added to this cooled solution, followed by reaction for 3 hours. Thereafter, 10 ml of an aqueous sodium hydrogen-carbonate solution was added to terminate the reaction. The reaction mixture was filtered through Celite and extracted with two 20 ml portions of diethyl ether and two 20 ml portions of ethyl acetate, and the extract was dried over anhydrous magnesium sulfate. Then, the solvents were distilled off, and hexane was added to the residue to crystallize binaphthol. The remaining solution was purified by means of silica gel column chromatography to obtain 0.16 g of methyl (S)-2- hydroxy-3-(1-cyclohexenyl)propionate. The yield was 89%.

1. customInto a 25-ml flask was placed
2. additionwere further added
3. customto prepare an (R)-binaphtholdibromotitanium complex
4. additionwere added to this cooled solution
5. customfollowed by reaction for 3 hours
6. customto terminate
7. customthe reaction
8. filtrationThe reaction mixture was filtered through Celite
9. extractionextracted with two 20 ml portions of diethyl ether and two 20 ml portions of ethyl acetate
10. dry with materialthe extract was dried over anhydrous magnesium sulfate
11. distillationThen, the solvents were distilled off
12. additionhexane was added to the residue
13. customto crystallize binaphthol
14. customThe remaining solution was purified by means of silica gel column chromatography

ORD record

ord-5424b0bf558d4fe98f558c49abc2f47a

Source dataset

uspto-grants-1990_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04965398