Catalytic asymmetric hetero-Diels–Alder route to a key intermediate for the synthesis of calyxin L

Abstract

A catalytic asymmetric formal synthesis of diarylheptanoid natural product calyxin L has been achieved by incorporating an enantio- and diastereoselective hetero-Diels–Alder (HDA) reaction, a Suzuki–Miyaura coupling, and a stereocontrolled catalytic hydrogenation of 2,4,6-trisubstituted dihydropyran as the key steps. The HDA reaction between 4-(4-benzyloxyphenyl)-2-triethylsilyloxy-1,3-butadiene and (4-benzenesulfonyloxyphenyl)propynal catalyzed by dirhodium(II) tetrakis[( R)-3-(benzene-fused-phthalimido)-2-piperidinonate], Rh 2( R-BPTPI) 4, provided cis-2,6-disubstituted tetrahydropyran-4-one in 91% yield with 91% ee.