Levine Samantha R, Krout Michael R, Stoltz Brian M
The Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Org Lett. 2009 Jan 15;11(2):289-92. doi: 10.1021/ol802409h.
A catalytic enantioselective approach to the eudesmane sesquiterpenoids is reported. The strategic use of a palladium-catalyzed enantioselective alkylation of vinylogous ester substrates forged the C(10) all-carbon quaternary center. This key transformation enabled a diastereoselective olefin hydrogenation to create the syn stereochemistry at C(7). The devised synthetic strategy allowed for the preparation of the antibacterial agent (+)-carissone and a formal synthesis of the P/Q-type calcium channel blocker (-)-alpha-eudesmol.
报道了一种催化对映选择性合成桉烷倍半萜类化合物的方法。通过钯催化的对映选择性烯醇酯底物烷基化的策略性应用,构建了C(10)全碳季碳中心。这一关键转化实现了非对映选择性烯烃氢化反应,在C(7)位形成顺式立体化学结构。所设计的合成策略可用于制备抗菌剂(+)-卡里松,并完成P/Q型钙通道阻滞剂(-)-α-桉叶醇的形式合成。