5-甲基-[(2E,6E)-3,7,11-三甲基-9-氧代十二碳二烯]苯醌和氢醌的首次全合成

以2-甲基对苯二酚和香叶基溴为起始原料, 经过酚羟基保护, 溴代, Li₂CuCl₄催化的芳基溴与Grignard试剂的偶联以及Julia偶联等一系列反应, 完成了裸鳃亚动物的代谢产物, 5-甲基-[(2E,6E)-3,7,11-三甲基-9-氧代十二碳二烯]苯醌(1)和氢醌(2)的首次全合成, 将1用NaBH₄还原, 得到(±)-3, (±)-3也是此类天然产物之一.

First Total Synthesis of 5-Methyl-2-(2E,6E-3,7,11-trimethyl-2,6-dodecadien-9-onyl)benzo-1,4-quinone and the Corresponding Hydroquinone

First total synthesis of triprenylquinones and hydroquinones isolated from endemic nudibranch Leminda millecra, two naturally occurring compounds 5-methyl-2-(2E,6E-3,7,11-trimethyl-2,6-dodecadien-9- onyl)benzo-1,4-quinone (1) and 5-methyl-2-(2E,6E-3,7,11-trimethyl-2,6-dodecadien-9-onyl)-1,4-hydroquinone (2) has been achieved from cheap and available 2-methylhydroquinone (4) and geranyl bromide, involving protection of phenol, bromination, coupling reaction of arylbromide with Grignard reagent catalyzed by Li₂CuCl₄, Julia coupling, etc. Reduction of 1 with NaBH₄, gave one of this kind of natural products, 5-methyl-2-(2E,6E-9-hydroxy-3,7,11-trimethyl-2,6-dodecadienyl)-1,4-hydroquinone (±)-3.