Stereoselective Synthesis of Highly Substituted 1,3-Dienes via "à la carte" Multifunctionalization of Borylated Dendralenes
Despite the high relevance of 1,3-dienes, stereoselective methods to access tetrasubstituted conjugated dienes are still scarce. We here report an efficient and modular approach that provides access to multifunctional tetrasubstituted 1,3-dienes with excellent levels of regio- and stereoselectivity. This methodology is based on a tetracomponent reaction between a borylated dendralene, an organolithium reagent and two different electrophiles. Mechanistic studies reveal that this transformation proceeds through a regio- and stereoselective carbolithiation/electrophilic trapping of an in situ formed dendralenic boron-ate complex, followed by a stereoretentive halodeborylation. The ease in which complex structural dienes can be accessed and their synthetic versatility highlight the importance and utility of this method ; Financial support from the AEI (CTQ2017-88451-R), Xunta de Galicia (ED431C 2018/04; Centro singular de investigación de Galicia accreditation 2019–2022, ED431G 2019/03) and the European Union (European Regional Development Fund—ERDF) is gratefully acknowledged. E. R.-C. thanks Xunta de Galicia for a predoctoral fellowship ; SI