Title | Second-Generation Synthesis of the Northern Fragment of Mandelalide A: Role of π-Stacking on Sharpless Dihydroxylation of -Enynes. |
Publication Type | Journal Article |
Year of Publication | 2019 |
Authors | Ghosh A, Brueckner AC, Cheong PHa-Yeon, Carter RG |
Journal | J Org Chem |
Volume | 84 |
Issue | 14 |
Pagination | 9196-9214 |
Date Published | 2019 07 19 |
ISSN | 1520-6904 |
Abstract | The development of a π-stacking-based approach for increased stereoselectivity in Sharpless asymmetric and diastereomeric dihydroxylation of -enynes is disclosed. The use of neighboring, electron-rich benzoate esters proved key to the success of this process. Density functional theory study suggests that the substrate benzoate ester group rigidifies the dihydroxylation transition states by forming a favorable π-stacking interaction in both and . The energetic preference for the was found in part because of the favorable eclipsing conformation of the alkene substituent as opposed to the disfavored bisecting conformation found in the . The application to a second-generation synthesis of the C15-C24 northern portion of mandelalide A is demonstrated. |
DOI | 10.1021/acs.joc.9b01153 |
Alternate Journal | J Org Chem |
PubMed ID | 31264876 |