TY - JOUR AU - Arseniyadis, Stellios; Fournier, Jérémy; Thangavelu, Saravanan; Lozano, Oscar; Prevost, Sébastien; Archambeau, Alexis; Menozzi, Candice; Cossy, Janine TI - Palladium-Catalyzed Allylic Alkylation of Allyl Dienol Carbonates: Reactivity, Regioselectivity, Enantioselectivity, and Synthetic Applications SN - 0936-5214 SN - 1437-2096 PY - 2013 JO - Synlett JF - Synlett LA - EN VL - 24 IS - 18 SP - 2350 EP - 2364 ET - 2013/10/18 DA - 2013/10/25 KW - palladium KW - allylations KW - alkylations KW - carbonates KW - heterocycles KW - total synthesis KW - natural products AB - For the past several years, the group has focused on the development of useful synthetic tools and on executing creative and efficient routes to biologically active natural products. In this context, we recently applied the palladium-catalyzed decarboxylative allylic alkylation reaction to a new class of substrates, namely allyl dienol carbonates. This method allowed a particularly straightforward access to a wide variety of heterocycles, including 2,4-disubstituted-, 2,3,4- and 2,3,5-trisubstituted-, and 2,3,4,5-tetrasubstituted furans and pyrroles, starting from simple and readily available substrates. An asymmetric version of this method was also developed and applied to the synthesis of enantiomerically enriched butenolides and butyrolactones bearing all-carbon α- and β-quaternary stereogenic centers, respectively. This asymmetric transformation was eventually used as a key step in the total synthesis of two natural products: (–)-nephrosteranic acid and (–)-roccellaric acid. This account summarizes the results of our endeavors.1 Introduction2 Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allyl Dienol Carbonates2.1 Synthesis of Polysubstituted Furans2.2 Synthesis of Polysubstituted Pyrroles3 Asymmetric Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allyl Dienol Carbonates3.1 Synthesis of Enantiomerically Enriched Butenolides3.2 Synthesis of Enantiomerically Enriched Furanones3.3 Synthesis of Enantiomerically Enriched Butyrolactones3.4 Total Syntheses of (–)-Nephrosteranic Acid and (–)-Roccellaric Acid4 Conclusion PB - © Georg Thieme Verlag DO - 10.1055/s-0033-1338987 UR - http://www.thieme-connect.de/products/ejournals/abstract/10.1055/s-0033-1338987 ER -