Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst.
J Org Chem
; 86(11): 7450-7459, 2021 06 04.
Article
en En
| MEDLINE
| ID: mdl-33999638
ABSTRACT
The desymmetrization of ten prochiral diols by phosphoryl transfer with a titanium-BINOLate complex is discussed. The phosphorylation of nine 1,3-propane diols is achieved in yields of 50-98%. Enantiomeric ratios as high as 928 are achieved with diols containing a quaternary C-2 center incorporating a protected amine. The chiral ligand, base, solvent, and stoichiometry are evaluated along with a nonlinear effect study to support an active catalyst species that is oligomeric in chiral ligand. The use of pyrophosphates as the phosphorylating agent in the desymmetrization facilitates a user-friendly method for enantioselective phosphorylation with desirable protecting groups (benzyl, o-nitrobenzyl) on the phosphate product.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Titanio
/
Alcoholes
Idioma:
En
Revista:
J Org Chem
Año:
2021
Tipo del documento:
Article
País de afiliación:
Estados Unidos