Synthesis of Enantiopure ε-Oxapipecolic Acid.
| Autor: | Howard EH; Department of Chemistry , University of South Florida , Tampa , Florida 33620 , United States., Cain CF; Department of Chemistry & Biochemistry , University of Notre Dame , Notre Dame , Indiana 46556 , United States., Kang C; Department of Chemistry , University of South Florida , Tampa , Florida 33620 , United States., Del Valle JR; Department of Chemistry & Biochemistry , University of Notre Dame , Notre Dame , Indiana 46556 , United States. |
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| Jazyk: | angličtina |
| Zdroj: | The Journal of organic chemistry [J Org Chem] 2020 Feb 07; Vol. 85 (3), pp. 1680-1686. Date of Electronic Publication: 2019 Nov 08. |
| DOI: | 10.1021/acs.joc.9b02382 |
| Abstrakt: | A six-step synthesis of orthogonally protected ( S )-ε-oxapipecolic acid is described, starting from a commercially available glutamate diester. The approach features m CPBA-mediated amine oxidation and an intramolecular Mitsunobu reaction to form the tetrahydrooxazine ring. The enantiopure building block was employed in the synthesis of a short model peptide to determine the amide rotamer preference N -terminal to the cyclic residue. In contrast to pipecolic acid, which exhibits a high cis amide population, the ε heteroatom in oxapipecolic acid exerts a strong trans substantiating effect through lone pair repulsion. |
| Databáze: | MEDLINE |
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