Stereocontrolled synthesis of Z-dienes via an unexpected pericyclic cascade rearrangement of 5-amino-2,4-pentadienals.
Donor-acceptor dienes known as Zincke aldehydes, which derive readily from the ring-opening reactions of pyridinium salts with secondary amines, undergo a fascinating thermal rearrangement reaction to afford Z-alpha,beta,gamma,delta-unsaturated amides with excellent stereoselectivity. Efficient, stereocontrolled access to Z-trisubstituted alkenes with two different substitution patterns is possible in three steps beginning with the appropriately substituted pyridine derivative. Preliminary studies have shown that both the amide and the monosubstituted alkene termini can be selectively functionalized. Ease of access, generality of scope, and facile product manipulation render this process attractive for the synthesis of complex polyenes.
Steinhardt
Sarah E
SE
Department of Chemistry, The University of California, Irvine, California 92697-2025, USA.
Silverston
Joel S
JS
Vanderwal
Christopher D
CD
D000447:Aldehydes / Q000138:chemical synthesis*; D009578:Nitrobenzenes / Q000737:chemistry*; D011090:Polyenes / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000447:Aldehydes; D009578:Nitrobenzenes; D011090:Polyenes