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Short Enantioselective Total Synthesis of Tatanan A and 3‐ epi ‐Tatanan A Using Assembly‐Line Synthesis
Author(s) -
Noble Adam,
Roesner Stefan,
Aggarwal Varinder K.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201609598
Subject(s) - stereocenter , chemistry , enantioselective synthesis , stereoselectivity , borylation , stereospecificity , total synthesis , stereochemistry , epimer , natural product , substrate (aquarium) , combinatorial chemistry , organic chemistry , catalysis , aryl , oceanography , geology , alkyl
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.