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Catalytic Asymmetric Synthesis of Geminal-Dicarboxylates

preprint
submitted on 19.04.2018 and posted on 20.04.2018 by Nisha Mistry, Stephen P. Fletcher

Stereogenic acetals, spiroacetals and ketals are well-studied stereochemical features that bear two heteroatoms at a common carbon atom. These stereocenters are normally found in cyclic structures while linear (or acyclic) analogues bearing two heteroatoms are rare. Chiral geminal-dicarboxylates are illustrative, there is no current way to access this class of compounds while controlling the stereochemistry at the carbon center bound to two oxygen atoms. Here we report a rhodium-catalyzed asymmetric carboxylation of ester-containing allylic bromides to form stereogenic carbon centers bearing two different carboxylates with high yields and enantioselectivities. The products, which are surprisingly stable to a variety of acidic and basic conditions, can be manipulated with no loss of enantiomeric purity as demonstrated be ring closing metathesis reactions to form chiral lactones, which have been extensively used as building blocks in asymmetric synthesis.

Funding

EPSRC

History

Email Address of Submitting Author

nisha.mistry@chem.ox.ac.uk

Email Address(es) for Other Author(s)

stephen.fletcher@chem.ox.ac.uk

Institution

University of Oxford

Country

United Kingdom

ORCID For Submitting Author

0000-0001-7543-5541

Declaration of Conflict of Interest

No conflicts of interest

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