Biomimetic enantioselective total synthesis of (-)-siccanin via the Pd-catalyzed asymmetric allylic alkylation (AAA) and sequential radical cyclizations.
Biomimetic enantioselective total synthesis of (-)-siccanin via the Pd-catalyzed asymmetric allylic alkylation (AAA) and sequential radical cyclizations.
复制标题
通过 Pd 催化的不对称烯丙基烷基化 (AAA) 和连续自由基环化，仿生对映选择性全合成 (-)-siccanin。
DOI：
10.1021/ja048084p
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
Surivet,Jean-Philippe
中科院分区：
文献类型：
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作者：
Trost,BarryM;Shen,HongC;Surivet,Jean-Philippe
（-）-Siccanin（1）是一种具有显著抗真菌活性的天然产物，通过仿生途径对映选择性地合成。该合成路线具有两个连续的自由基环化：环氧烯烃48的Ti（III）介导的自由基环化以构建B环，以及苏亚雷斯反应以建立四氢呋喃环。基于我们最近研究的钯催化的苯酚三取代烯丙基碳酸酯的不对称烯丙基烷基化反应（AAA），制备了茜卡宁的手性色满部分。还合成了siccanin家族的几个其他成员，包括siccanochromene A（2）、B（3）、E（6）、F（7）和siccanochromene C的甲基醚（55）。这些研究可能有助于了解这一新家族化合物的生物合成。
(−)-Siccanin (1), a natural product possessing significant antifungal properties, was synthesized enantioselectively via a biomimetic route. This synthetic route features two sequential radical cyclizations: a Ti(III)-mediated radical cyclization of epoxyolefin48to construct the B-ring, and a Suarez reaction to establish the tetrahyrofuran ring. Chiral chroman moiety of siccanin was prepared based on our recent development of the Pd-catalyzed asymmetric allylic alkylation (AAA) of phenol trisubstituted allyl carbonates. Several other members of the siccanin family were also synthesized including siccanochromenes A (2), B (3), E (6), F (7), and the methyl ether of siccanochromene C (55). These studies may shed light on the biosynthesis of this novel family of compounds.