Construction of <i>trans</i>-2,6-DisubstitutedPiperidine Skeleton and Its Application to the Total Synthesis of(−)-Myrtine and <i>trans</i>-Piperidine-Type Poison-FrogAlkaloids

We have succeeded in constructing a <i>trans</i>-2,6-<u>d</u>isubstituted <u>p</u>iperidine (<i>trans-2</i>,6-DP) skeleton by treatment of allylsilane derivative <b>2</b> with TMSOTf. Our designed <i>trans-2</i>,6-DP <b>1</b> has oxygen functional groups at the 2- and 6-positions and an <i>exo</i>-methylene moiety at the 4-position and is expected to be applied not only to the synthesis of various natural products but also as an excellent chiral building block with <i>pseudo</i>-symmetry. To demonstrate the versatility of <b>1</b>, the total synthesis of (−)-myrtin and <i>trans</i>-piperidine-type poison-frog alkaloid <b>213A</b> and <b>213B</b> was accomplished.