Abstract
Here we present a polycyclization of oxotriphenylhexanoates. The polycyclization is governed by electronic effects, and three major synthetic paths have been established leading to stereochemically complex tricyclic frameworks with up to five stereogenic centers. The method is compatible with an array of functional groups, allowing pharmacophoric elements to be introduced post cyclization.
Highlights
M orphine,[1] paclitaxel,[2−4] strychnine,[5] or polycyclic terpenes[6,7] are some examples of natural polycyclic products containing a complex ring system with several stereogenic centers
Polycyclic compounds are interesting because they encode a high degree of molecular information that often makes them selective for a particular biological target
A number of cascade polycyclizations in natural product synthesis[21,22] have been designed relying on dearomatizariondriven,[23] pericyclic,[24−32] cationic,[33−40] metal-catalyzed,[41−48] and radical cascades.[49−58] Inspired by these strategies, we began investigating the possibility for cyclizing the oxotriphenylhexanoate (OTHO) core
Summary
6f with allylmagnesium bromide in the presence of silver nitrate gave the corresponding bis-allylated product,[66] which in turn was directly used in a palladium-catalyzed Suzuki crosscoupling reaction[67] yielding the doubly functionalized compound 7 in 42% yield, over two steps, as a single diastereomer. A systematic investigation of the aromatic substitution pattern of the OTHOs shows that the cyclization is under aromatic electronic control directing the cyclization reaction to either tricyclic molecule 3 or bridgehead dibromo derivative 6. Both types of compound classes are difficult to prepare by any other known methodologies and can potentially be used to position functional groups in space vital, for instance, in the design of biologically active compounds. Martin Kamlar − Department of Chemistry and Chemical Engineering, Chalmers University of Technology, 412 96 Gothenburg, Sweden; Department of Organic Chemistry, Faculty of Science, Charles University, 128 43 Prague 2, Czech Republic.
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