Reacción #155471

Ecuación de reacción

1,4-dioxaspiro[4.5]decan-8-one

methyl 2-(benzyloxycarbonylamino)-2-(dimethoxyphosphoryl)acetate

1,1,3,3-tetramethylguanidine

→

methyl 2-(benzyloxycarbonylamino)-2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetate

Rendimiento 26.8%

Disolventes

EtOAc

EtOAc

EtOAc

Condiciones de reacción

Tratamiento posterior

1. 1
   LavadoThe organic layer was washed with 1N HCl (75 mL), H2O (100 mL) and brine (100 mL)
2. 2
   Secadodried (MgSO4)
3. 3
   Filtraciónfiltered
4. 4
   Concentraciónconcentrated
5. 5
   OtroThe residue was purified via Biotage (5% to 25% EtOAc/Hexanes; 300 g column)
6. 6
   workup.ADDITIONThe combined fractions containing the product
7. 7
   Concentraciónwere then concentrated under vacuum
8. 8
   Otrothe residue was re-crystallized from hexanes/EtOAc

Procedimiento

A solution of 1,4-dioxaspiro[4.5]decan-8-one (15 g, 96 mmol) in EtOAc (150 mL) was added to a solution of methyl 2-(benzyloxycarbonylamino)-2-(dimethoxyphosphoryl)acetate (21.21 g, 64.0 mmol) in 1,1,3,3-tetramethylguanidine (10.45 mL, 83 mmol) and EtOAc (150 mL). The resulting solution was the stirred at ambient temperature for 72 h and then it was diluted with EtOAc (25 mL). The organic layer was washed with 1N HCl (75 mL), H2O (100 mL) and brine (100 mL), dried (MgSO4), filtered and concentrated. The residue was purified via Biotage (5% to 25% EtOAc/Hexanes; 300 g column). The combined fractions containing the product were then concentrated under vacuum and the residue was re-crystallized from hexanes/EtOAc to give white crystals that corresponded to methyl 2-(benzyloxycarbonylamino)-2-(1,4-dioxaspiro[4.5]decan-8-ylidene)acetate (6.2 g) 1H NMR (400 MHz, CDCl3-d) δ ppm 7.30-7.44 (5H, m), 6.02 (1H, br. s.), 5.15 (2H, s), 3.97 (4H, s), 3.76 (3H, br. s.), 2.84-2.92 (2H, m), 2.47 (2H, t, J=6.40 Hz), 1.74-1.83 (4H, m). LC (Cond. OL1): Rt=2.89 min. LC/MS: Anal. Calcd. For [M+Na]+ C19H23NNaO6: 745.21. found: 745.47.

Fuente