A catalytic asymmetric total synthesis of (−)-perophoramidine. Issue 1 (22nd August 2014)

• Record Type: Journal Article
• Authors: Trost, B. M.; Osipov, M.; Krüger, S.; Zhang, Y.
• Is Part Of: Chemical science. Volume 6:Issue 1(2015:Jan.)
• Page Start: 349
• Page End: 353
• Publication Date: 2014-08-22
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c4sc01826e
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : We describe a catalytic asymmetric total synthesis of the ascidian alkaloid (−)-perophoramidine employing a Mo-catalyzed asymmetric allylic alkylation and unprecedented imino ether allylation as key steps. Abstract : We report a catalytic asymmetric total synthesis of the ascidian natural product perophoramidine. The synthesis employs a molybdenum-catalyzed asymmetric allylic alkylation of an oxindole nucleophile and a monosubstituted allylic electrophile as a key asymmetric step. The enantioenriched oxindole product from this transformation contains vicinal quaternary and tertiary stereocenters, and is obtained in high yield along with high levels of regio-, diastereo-, and enantioselectivity. To install the second quaternary stereocenter in the target, the route utilizes a novel regio- and diastereoselective allylation of a cyclic imino ether to deliver an allylated imino ether product in near quantitative yield and with complete regio- and diastereocontrol. Oxidative cleavage and reductive amination are used as final steps to access the natural product.