Division of Environmental Materials Science, Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0810, Japan.
Org Lett. 2010 Mar 5;12(5):904-7. doi: 10.1021/ol9027336.
The first enantioselective total synthesis of 10-isocyano-4-cadinene, a marine sesquiterpene isolated from nudibranchs of the family Phyllidiidae, was achieved. The cadinene is expected to be a novel nontoxic antifouling agent. In the synthesis, an intermolecular Diels-Alder reaction and a SmI(2)-induced Barbier-type reaction were employed as key steps. The absolute configuration of 10-isocyano-4-cadinene was determined to be (1S, 6S, 7R, 10S) on the basis of the total synthesis. Antifouling activities against Balanus amphitrite with both enantiomers of 10-isocyano-4-cadinene were also evaluated.
首次实现了从裸鳃目海兔科分离得到的海洋倍半萜 10-异氰酸基-4-卡烯的对映选择性全合成。该卡烯有望成为一种新型无毒防污剂。在合成中，采用了分子间 Diels-Alder 反应和 SmI(2)诱导的 Barbier 型反应作为关键步骤。基于全合成，确定 10-异氰酸基-4-卡烯的绝对构型为(1S, 6S, 7R, 10S)。还评估了两种对映体 10-异氰酸基-4-卡烯对藤壶的防污活性。
