To further explore the catalytic potentials of the present methodology, we applied this reaction to the total synthesis of plecarpenene and plecarpenone (Figure ), two guaiane natural sesquiterpenoids isolated from Pleocarphus revolutus in 1976. Due to the lacking of an efficient strategy for the preparation of bicyclo[5.3.0]decane ring systems, only the Snapper group has reported their total synthesis so far. First, ester 3p was subjected to a decarboxylation reaction under the Tsuji conditions to afford the desired ketone 4 in 76% yield. Ketone 4 was then reduced by NaBH4 followed by a treatment with excess of MeLi to produce the olefin 5 in 86% yield over 2 steps. With sufficient quantity of olefin 5 in hand, we next sought to saturate the olefin group to install the last stereo-center of the natural product. However, elaboration of olefin 5 was shown to be highly challenging. As outlined in Table , the saturation of olefin 5 with conventional hydrogenation reaction using Pd/C as the catalyst failed to give the desired product due to the steric hindrance (Table , entry 1). Moreover, similar results were observed when Crabtree's or Wilkinson's catalyst was used (Table , entries 2 and 3). Unfortunately, further reaction condition screening revealed that hydrogenation using the highly reactive PtO2 (Table , entry 4) in ethyl acetate produced the undesired diastereomer 7 as the single product.