Enantioselective synthesis of 6,6-disubstituted pentafulvenes containing a chiral pendant hydroxy group

Nouch, Ryan; Cini, Melchior; Magre, Marc; Abid, Mohammed; Di�guez, Monserrat; P�mies, Oscar; Woodward, Simon; Lewis, William

Abstract

Simple enantioselective synthesis of 6,6-disubstituted pentafulvenes bearing chiral pendant hydroxy groups are attained by cascade reactivity using commercially available proline-based organocatalysts. Condensation of cyclopentadiene with the acetyl function of a 1,2-formylacetophenone, followed by cyclization of a resulting fulvene-stabilized carbanion with the formyl group, generates bicyclic chiral alcohols with initial er values up to 94:6. Exceptional enantio-enrichment of the resultant alcohols results upon crystallization – even near racemic samples spontaneously de-racemize. This enables new families of substituted cyclopentadienes that are both enantiomerically and diastereomerically pure to be rapidly attained.

Citation

Nouch, R., Cini, M., Magre, M., Abid, M., Diéguez, M., Pàmies, O., …Lewis, W. (in press). Enantioselective synthesis of 6,6-disubstituted pentafulvenes containing a chiral pendant hydroxy group. Chemistry - A European Journal, https://doi.org/10.1002/chem.201704247

• Journal Article Type: Article
• Acceptance Date: Oct 26, 2017
• Online Publication Date: Oct 30, 2017
• Deposit Date: Nov 1, 2017
• Publicly Available Date: Oct 31, 2018
• Journal: Chemistry - a European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• DOI: https://doi.org/10.1002/chem.201704247
• Public URL: https://nottingham-repository.worktribe.com/output/891038
• Publisher URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.201704247/abstract