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Split-and-pool Synthesis and Characterization of Peptide Tertiary Amide Library
Published on: June 20, 2014
Short Enantioselective Total Synthesis of Tatanan A and 3-epi-Tatanan A Using Assembly-Line Synthesis
Adam Noble1, Stefan Roesner1, Varinder K Aggarwal1
1School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
Abstract:
Short and highly stereoselective total syntheses of the sesquilignan natural product tatanan A and its C3 epimer are described. An assembly-line synthesis approach, using iterative lithiation-borylation reactions, was applied to install the three contiguous stereocenters with high enantio- and diastereoselectivity. One of the stereocenters was installed using a configurationally labile lithiated primary benzyl benzoate, resulting in high levels of substrate-controlled (undesired) diastereoselectivity. However, reversal of selectivity was achieved by using a novel diastereoselective Matteson homologation. Stereospecific alkynylation of a hindered secondary benzylic boronic ester enabled completion of the synthesis in a total of eight steps.
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