Ti(II) and Rh(I) complexes as reagents toward a thapsigargin core

Sanogo, Y., Othman, R. B., Dhambri, S., Selkti, M., Jeuken, A., Prunet, J. , Férézou, J.-P., Ardisson, J., Lannou, M.-I. and Sorin, G. (2019) Ti(II) and Rh(I) complexes as reagents toward a thapsigargin core. Journal of Organic Chemistry, 84(9), pp. 5821-5830. (doi: 10.1021/acs.joc.8b03249) (PMID:30964681)

Abstract

A novel approach toward the [5—7]fused bicyclic core of thapsigargin, a subnanomolar inhibitor of the endo/sarcoplasmic calcium ATPase (SERCA), is presented. The synthetic route includes an original Ti(II)-mediated hydroxy-directed reductive coupling of an enantiomerically enriched propargylic alcohol and an intramolecular Rh(I)-catalyzed cyclocarbonylation reaction as key steps. Interestingly, through the first experiments of titanocene-mediated reductive cyclization of a 1,8-enyne, a seven-membered cycle was isolated as a unique product with a total diastereoselectivity.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Jeuken, Mr Alan and Prunet, Dr Joelle
• Authors: Sanogo, Y., Othman, R. B., Dhambri, S., Selkti, M., Jeuken, A., Prunet, J., Férézou, J.-P., Ardisson, J., Lannou, M.-I., and Sorin, G.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Organic Chemistry
• Publisher: American Chemical Society
• ISSN: 0022-3263
• ISSN (Online): 1520-6904
• Published Online: 09 April 2019