One-step catalytic asymmetric synthesis of all-syn deoxypropionate motif from propylene: Total synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid
One-step catalytic asymmetric synthesis of all-syn deoxypropionate motif from propylene: Total synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid
复制标题
丙烯一步催化不对称合成全顺式脱氧丙酸酯基序：(2R,4R,6R,8R)-2,4,6,8-四甲基癸酸的全合成
DOI：
--
复制
发表时间：
2016
影响因子：
11.1
通讯作者：
K. Nozaki
中科院分区：
文献类型：
--
作者：
Y. Ota;Toshiki Murayama;K. Nozaki
迄今为止报道的脱氧丙酸基序的合成策略主要采用迭代延伸法，因此需要许多反应步骤才能获得所需的天然产物。此外，这种方法还需要准备复杂的构建块。本文通过立体控制丙烯低聚，一步构建了脱氧丙酸基序。我们的方法使用丙烯作为一个非常简单的构建块提供了最短的，三步获得天然产品，其制备通常需要至少10步。此外，从同一低聚产物中可以分离到具有不同脱氧丙酸单位数的多个低聚物，从而可以构建库。由于脱氧丙酸基序存在于多种生物活性化合物中，我们的方法将对合成有机化学领域产生影响。在自然界中，许多复杂的结构是由简单的分子通过一系列定制的酶催化反应组装而成的。一个代表性的例子是脱氧丙酸基序，它是一个含有多个立体中心的交替甲基化烷基链，由简单的构建块通过一系列酶促反应生物合成。然而，在有机合成中，大多数报道的途径需要合成复杂的构建块。此外，每次延伸都需要多步反应和单独的纯化。在这里，我们展示了从丙烯一步构建脱氧丙酸结构，以实现三步合成(2R,4R,6R,8R)-2,4,6,8-四甲基癸酸，这是灰雁腺蜡的主要酸成分。为了实现这一策略，我们重点研究了配位链转移聚合，并优化了反应条件，以获得立体控制的低聚物，这与迄今为止开发的其他合成策略形成了对比，这些合成策略每单元需要3-6步，并且不可避免地产生副产物。同时，从一批样品中分离出多个具有不同单位数的脱氧丙酸低聚物，在文库建设中具有一定的应用价值。我们的策略为其他具有脱氧丙酸基序的天然产物的简易合成途径打开了大门。
Significance Synthetic strategies for deoxypropionate motif reported to date mainly use iterative elongations, thus requiring many reaction steps to obtain the desired natural product. Additionally, such methods also require the preparation of complex building blocks. Here, we have developed a one-step construction of deoxypropionate motif by stereo-controlled propylene oligomerization. Our method using propylene as a very simple building block provides the shortest, three-step access to a natural product whose preparation conventionally required at least 10 steps. Furthermore, multiple oligomers with different number of deoxypropionate units can be isolated from the same oligomerization product, enabling the construction of library. Because deoxypropionate motif is found in a variety of biologically active compounds, our method would impact the field of synthetic organic chemistry. In nature, many complex structures are assembled from simple molecules by a series of tailored enzyme-catalyzed reactions. One representative example is the deoxypropionate motif, an alternately methylated alkyl chain containing multiple stereogenic centers, which is biosynthesized by a series of enzymatic reactions from simple building blocks. In organic synthesis, however, the majority of the reported routes require the syntheses of complex building blocks. Furthermore, multistep reactions with individual purifications are required at each elongation. Here we show the construction of the deoxypropionate structure from propylene in a single step to achieve a three-step synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid, a major acid component of a preen-gland wax of the graylag goose. To realize this strategy, we focused on the coordinative chain transfer polymerization and optimized the reaction condition to afford a stereo-controlled oligomer, which is contrastive to the other synthetic strategies developed to date that require 3–6 steps per unit, with unavoidable byproduct generation. Furthermore, multiple oligomers with different number of deoxypropionate units were isolated from one batch, showing application to the construction of library. Our strategy opens the door for facile synthetic routes toward other natural products that share the deoxypropionate motif.
影响因子：
15
作者：
Balieu, Sebastien;Hallett, Gayle E.;Aggarwal, Varinder K.
通讯作者：
Aggarwal, Varinder K.