Diallylamine → Cyanamide, diallyl

Temperature

0 °C

To a solution of 1-Boc-4-piperidone (2.61 g, 13.03 mmol) in 1,2-dichloroethane (25 mL) was added diallyl amine (1.7 mL, 13.77 mmol) and the mixture cooled to 0° C. Titanium(IV) isopropoxide (3.9 mL, 13.3 mmol) was then added and the reaction warmed to room temperature and stirred for 2.5 d. The resultant orange mixture was then cooled to 0° C. and diethylaluminum cyanide added (1 M in toluene, 16 mL, 16 mmol) The reaction was warmed to room temperature, stirred for 3.5 h then diluted with CH2Cl2 (30 mL) and EtOAc (25 mL). The mixture was cooled to 0° C., quenched with water (7 mL) and filtered through celite, washing with CH2Cl2 and MeOH. The resultant filtrate was concentrated, diluted with CH2Cl2 (150 mL), dried (Na2SO4), concentrated and purified by flash chromatography on silica gel (Hexanes/EtOAc, 3:1 then 1:1) to afford the diallylamino-cyanide intermediate (2.79 g, 70%) as a yellow oil.

1. temperaturethe reaction warmed to room temperature
2. temperatureThe resultant orange mixture was then cooled to 0° C.
3. temperaturewas warmed to room temperature
4. stirringstirred for 3.5 h
5. temperatureThe mixture was cooled to 0° C.
6. customquenched with water (7 mL)
7. filtrationfiltered through celite
8. washwashing with CH2Cl2 and MeOH
9. concentrationThe resultant filtrate was concentrated
10. additiondiluted with CH2Cl2 (150 mL)
11. dry with materialdried (Na2SO4)
12. concentrationconcentrated
13. custompurified by flash chromatography on silica gel (Hexanes/EtOAc, 3:1

ORD record

ord-c86bd446f042426cb1418bc66eb73cf6

Source dataset

uspto-grants-2011_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07863293B2