Reaktion #345348

ord-4a22e42a6b104e72b02fc377584c65da

Reaktionsgleichung

CCOC(C)=O.O.[Cl-].[Na+]
brine EtOAc
CCOC(=O)CN=[N+]=[N-]
ethyl α-azidoacetate
CC(C)(C)OP(=O)(OC(C)(C)C)C(O)c1ccc(C=O)cc1
4-[bis(tert-butoxy) -phosphorylhydroxymethyl)benzaldehyde
C[O-].[Na+]
NaOMe
→
COC(=O)C(=Cc1ccc(C(O)P(=O)(OC(C)(C)C)OC(C)(C)C)cc1)N=[N+]=[N-]
7
COC(=O)C(=Cc1ccc(C(O)P(=O)(OC(C)(C)C)OC(C)(C)C)cc1)N=[N+]=[N-]
Methyl α-azido-4-[bis(tert-butoxy)phosphorylhydroxymethyl]cinnamate

Edukte

CCOC(C)=O.O.[Cl-].[Na+]
brine EtOAc
CCOC(=O)CN=[N+]=[N-]
ethyl α-azidoacetate
CC(C)(C)OP(=O)(OC(C)(C)C)C(O)c1ccc(C=O)cc1
4-[bis(tert-butoxy) -phosphorylhydroxymethyl)benzaldehyde
C[O-].[Na+]
NaOMe

Reagenzien

Keine

Lösungsmittel

CO
MeOH
CO
MeOH

Reaktionsbedingungen

Temperatur
-78°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    Sonstigean additional 1 hour
  2. 2
    Sonstigeat 0° C
  3. 3
    Sonstigeto yield a light yellow crystalline solid, which
  4. 4
    Sonstigewas triturated with CHCl3 /pet. ether (35°-60° C.)

Vorschrift

To a solution of 6.45 g (50 mmol) of ethyl α-azidoacetate and 1.64 g (5.0 mmol) of 4-[bis(tert-butoxy) -phosphorylhydroxymethyl)benzaldehyde 6 in MeOH (20 mL) at -78° C. was added a total of 7.4 mL (40 mmol) of NaOMe, 5.4M in MeOH, dropwise over 5 minutes. The mixture was stirred 5 minutes at -78° C. then an additional 1 hour at 0° C. The resulting light yellow suspension was subjected to an extractive work up (brine/EtOAc) to yield a light yellow crystalline solid, which was triturated with CHCl3 /pet. ether (35°-60° C.) to yield 7 as light yellow crystals, 1.26 g (57%), mp 111°-113° C.

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05264607uspto-grants-1993_11