Methanol → (1r)-Acetic acid n'-(1-phenyl-but-3-enyl)-hydrazide

Enantioselective allylation of acetic acid benzylidene-hydrazide (8) to give (1R)-acetic acid N′-(1-phenyl-but-3-enyl)-hydrazide: To a cooled (10° C.) solution of (4S,5S)-2-Allyl-2-chloro-3,4-dimethyl-5-phenyl-[1,3,2]oxazasilolidine (9.90 g, 37.0 mmol) in CH2Cl2 (300 mL) was added acetic acid benzylidene-hydrazide (5.00 g, 30.8 mol) as a solid. The resulting solution was stirred for 16 hours and methanol (40 mL) was then added. After 15 min all volatiles were removed by distillation and the residue was diluted with EtOAc (150 mL) and H2O (500 mL). The phases were separated and the aqueous layer was extracted with EtOAc (2×150 mL). The combined organic layers were washed with H20 and brine, dried (MgSO4), filtered and concentrated. Analysis of the residue by HPLC revealed an ee of 87%. The residue was dissolved in boiling toluene (80 mL) and the solution was then cooled to ambient temperature. Pentane (380 mL) was layered on top of the toluene solution and the resulting biphasic solution was allowed to stand for 16 hours. The resulting crystalline solid precipitate was filtered, washed (pentane:toluene (5:1)) and then dried in vacuo to give 5.04 g (80%) of (1R)-acetic acid N′-(1-phenyl-but-3-enyl)-hydrazide in 98% ee.

1. customAfter 15 min all volatiles were removed by distillation
2. additionthe residue was diluted with EtOAc (150 mL) and H2O (500 mL)
3. customThe phases were separated
4. extractionthe aqueous layer was extracted with EtOAc (2×150 mL)
5. washThe combined organic layers were washed with H20 and brine
6. dry with materialdried (MgSO4)
7. filtrationfiltered
8. concentrationconcentrated
9. dissolutionThe residue was dissolved
10. waitto stand for 16 hours
11. filtrationThe resulting crystalline solid precipitate was filtered
12. washwashed (pentane:toluene (5:1))
13. customdried in vacuo

ORD record

ord-01d0f8eb13f94e938c445ac549cf7f60

Source dataset

uspto-grants-2009_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07534905B2