Construction of trans-2,6-Disubstituted Piperidine Skeleton and Its Application to the Total Synthesis of (−)-Myrtine and trans-Piperidine-Type Poison-Frog Alkaloids

We have succeeded in constructing a trans-2,6-disubstituted piperidine (trans-2,6-DP) skeleton by treatment of allylsilane derivative 2 with TMSOTf. Our designed trans-2,6-DP 1 has oxygen functional groups at the 2- and 6-positions and an exo-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 pseudo-symmetry. To demonstrate the versatility of 1, the total synthesis of (-)-myrtin and trans-piperidine-type poison-frog alkaloid 213A and 213B was accomplished.