Beschreibung:
<jats:p><jats:bold>Synthesis of Plagiochins A and B, Macrocyclic Bis(bibenzyl) Ethers from <jats:italic>Plagiochila acantophylla</jats:italic></jats:bold></jats:p><jats:p>Plagiochins A (<jats:bold>1</jats:bold>) and B (<jats:bold>2</jats:bold>), macrocyclic bis(bibenzyl) ethers with a 16‐membered ring, are synthesized. The key steps are the Pd(0)‐catalyzed C—C coupling of an areneboronic acid (<jats:bold>18</jats:bold>) with an aryl bromide with formation of a biphenyl (<jats:bold>13</jats:bold>), Ullmann ether synthesis of a diphenyl ether (<jats:bold>23</jats:bold>), Wittig reaction to connect the two components <jats:bold>13</jats:bold> and <jats:bold>23</jats:bold>, and a modified Wurtz reaction to close the ring. The latter reaction is accompanied by an unusual transformation of a <jats:italic>C</jats:italic>‐benzyloxy to a <jats:italic>C</jats:italic>‐benzoyl group.</jats:p>