Experimental and theoretical studies on the Nazarov cyclization/Wagner-Meerwein rearrangement sequence.

ABSTRACT: Highly functionalized cyclopentenones can be generated by a chemoselective copper(II)-mediated Nazarov/Wagner-Meerwein rearrangement sequence of divinyl ketones. A detailed investigation of this sequence is described including a study of substrate scope and limitations. After the initial 4π electrocyclization, this reaction proceeds via two different sequential [1,2]-shifts, with selectivity that depends upon either migratory ability or the steric bulkiness of the substituents at C1 and C5. This methodology allows the creation of vicinal stereogenic centers, including adjacent quaternary centers. This sequence can also be achieved by using a catalytic amount of copper(II) in combination with NaBAr(4)(f), a weak Lewis acid. During the study of the scope of the reaction, a partial or complet

SUBMITTER: Lebœuf D 

PROVIDER: S-EPMC3382077 | biostudies-literature | 2012 Apr

REPOSITORIES: biostudies-literature