Pd-Catalyzed Dienylation of Propargylic Esters Enabling Highly Stereoselective Synthesis of Danishefsky-Type Trisubstituted Dienes
Chen Zhou , Mengfu Dai , Xiaoyu Yin , Mingyue Zhang , Weijin Gu , Liang-An Chen
Chinese Journal of Chemistry ›› 2024, Vol. 42 ›› Issue (17) : 1993 -1998.
Pd-Catalyzed Dienylation of Propargylic Esters Enabling Highly Stereoselective Synthesis of Danishefsky-Type Trisubstituted Dienes
The stereochemical synthesis of highly substituted Danishefsky-type dienes remains unsolved in organic chemistry. We describe a simple and efficient approach for the stereoselective synthesis of Danishefsky-type trisubstituted dienes from readily available propargylic esters via Pd-catalyzed dienylation reaction through the key intermediate metallacyclobutene in a regio-, chemo- and stereoselective fashion. This method facilitates a broad range of challenging trisubstituted dienes with a high level of stereocontrol. The synthetic utilities of oxygenated trisubstituted dienes have been demonstrated by the downstream chemistry, which notably undergoes Diels-Alder reaction with a variety of electron-deficient dienophiles to furnish multisubstituted cyclohexenes in good yields with excellent stereoselectivity.
Propargylic ester / Dienylation / Diene / Stereoselectivity / Cycloaddition / Palladium / β-H elimination / Regioselectivity
2024 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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