Unexpected endo Selectivity of Conjugate Nucleophilic Addition to an Arene−Cr(CO)3 Complex: Enantioselective Synthesis of the Diterpene 11-epi-Helioporin B

[reaction: see text]. Starting from a nonracemic planar-chiral arene tricarbonyl chromium complex, an epimer of the bioactive marine diterpene helioporin B was synthesized in a highly stereoselective fashion. The stereostructure of the product (11-epi-helioporin B) corresponds to that of other serrulatane-type natural products. In a key step of the synthesis, 2-lithioacetonitrile undergoes conjugate nucleophilic addition to an unsaturated complex. Remarkably, this addition occurs in an endo mode, i.e., from the complexed face of the pi-ligand.