Phenylsilane → HCID 15250487, compound

Temperature

0 °C

In a dry sealable Schlenk flask under an argon atmosphere 0.0573 g (0.096 mmol) of (S,S)-ethylene-1,2-bis(η5 -4,5,6,7-tetrahydro-1-indenyl)titanium (S)-1,1'-binaphth-2,2'-diolate was dissolved in THF (10 mL). The vessel was degassed by exposure to vacuum (2 x~10 sec) and put under an atmosphere of hydrogen and subsequently cooled to 0° C. in an ice water bath. After equilibration, a solution of n-butyllithium (0.123 mL, 1.52M in hexanes, 0.187 mmol, 1.95 equiv) was added and the mixture was allowed to stir for 10 min. Phenylsilane (0.030 mL, 0.236 mmol, 2.4 equiv) was then added followed, after 5 minutes, by E-3-(4-methoxyphenyl)-2-methyl-1-methoxy-2-propene (0.345 g, 1.92 mmol, 20 equiv). The flask was sealed and the solution moved into a dry box and transferred to a Parr® high pressure reaction vessel containing a magnetic stir bar. The vessel was sealed and moved to a fume hood where it was charged to ~2000 psig with hydrogen and placed in an oil bath at 65° C. The reaction mixture was allowed to stir for 43.5 h. The vessel was cooled to room temperature, vented and opened to air. The reaction mixture was worked up by partitioning between diethyl ether/hexane (1/4) and water and separating the layers. The aqueous layer was extracted twice with ether/hexane and the combined organic layers were dried over MgSO4. The solvent was removed in vacuo and the residue distilled at reduced pressure to yield 0.225 g (1.42 mmol, 74%) of 3-(4-methoxyphenyl)-2-methyl-1-methoxypropane which had an ee of 92.7%.

1. customThe vessel was degassed by exposure to vacuum (2 x~10 sec)
2. customThe flask was sealed
3. customthe solution moved into a dry box
4. customtransferred to a Parr® high pressure reaction vessel
5. additioncontaining a magnetic stir bar
6. customThe vessel was sealed
7. customplaced in an oil bath at 65° C
8. stirringto stir for 43.5 h
9. temperatureThe vessel was cooled to room temperature
10. customby partitioning between diethyl ether/hexane (1/4) and water
11. customseparating the layers
12. extractionThe aqueous layer was extracted twice with ether/hexane
13. dry with materialthe combined organic layers were dried over MgSO4
14. customThe solvent was removed in vacuo
15. distillationthe residue distilled at reduced pressure

ORD record

ord-cec6c4e773db4c2fa4a1dacc0ca7feeb

Source dataset

uspto-grants-1995_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05442119