Desymmetrization of Diols by Phosphorylation with a Titanium-BINOLate Catalyst

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 92:8 are achieved with diols containing a quaternary C-2 center incorporatin...

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Bibliographic Details
Published in:Journal of organic chemistry 2021-06, Vol.86 (11), p.7450-7459
Main Authors: Ouellette, Erik T, Lougee, Marshall G, Bucknam, Andrea R, Endres, Paul J, Kim, John Y, Lynch, Emma J, Sisko, Elizabeth J, Sculimbrene, Bianca R
Format: Article
Language:English
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Summary: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 92:8 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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.1c00414