Catalytic Dynamic Kinetic Resolutions in Tandem to Construct Two-Axis Terphenyl Atropisomers.
Catalytic Dynamic Kinetic Resolutions in Tandem to Construct Two-Axis Terphenyl Atropisomers.
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DOI：
10.1021/jacs.0c08057
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发表时间：
2020-09-23
影响因子：
15
通讯作者：
Miller SJ
中科院分区：
文献类型：
--
作者：
Beleh OM;Miller E;Toste FD;Miller SJ
具有多个立体轴的分子的定义结构与材料科学、药学和催化越来越相关。然而，控制多个立体发育轴的催化对映体选择性方法在综合上仍然具有挑战性。我们报道了两轴三苯基阿托品的催化合成，与氯化和溴化异构体具有互补的策略，形成了高的非对映和对映选择性。化学过程通过两个不同的动态动力学拆分序列进行：第一，布林曼型内酯的反常选择性开环产生具有一个已建立手性轴的产品；第二，立体选择性芳烃卤化提供具有第二手性轴的产品。为了实现这些结果，首次报道了一类能够催化有效的阿托品选择性氯化反应的Brnsted碱性金刚烷化多肽。此外，还报道了一种互补的溴化反应，这也建立了第二个立体轴。在发现C2-对称磷酸的手性阴离子相转移催化允许催化剂在第二个立体化学决定事件中控制之后，这些溴三苯是可获得的。因此，我们建立了所有可能的氯化立体异构体的完全催化剂控制的立体发散合成，同时在溴化变体中也显示了非对映发散，在两种情况下都具有显著的对映选择性水平。
The defined structure of molecules bearing multiple stereogenic axes is of increasing relevance to materials science, pharmaceuticals, and catalysis. However, catalytic enantioselective approaches to control multiple stereogenic axes remain synthetically challenging. We report the catalytic synthesis of two-axis terphenyl atropisomers, with complementary strategies to both chlorinated and brominated variants, formed with high diastereo- and enantioselectivity. The chemistry proceeds through a sequence of two distinct dynamic kinetic resolutions: first, an atroposelective ring-opening of Bringmann-type lactones produces a product with one established axis of chirality; second, a stereoselective arene halogenation delivers the product with the second axis of chirality established. In order to achieve these results, a class of Brønsted basic guanidinylated peptides, which catalyze an efficient atroposelective chlorination, is reported for the first time. In addition, a complementary bromination is reported, which also establishes the second stereogenic axis. These bromo-terphenyls are accessible following the discovery that chiral anion phase transfer catalysis by C2-symmetric phosphoric acids allows catalyst control in the second stereochemistry-determining event. Accordingly, we established the fully catalyst-controlled stereodivergent synthesis of all possible chlorinated stereoisomers, while also demonstrating diastereodivergence in the brominated variants, with significant levels of enantioselectivity in both cases.
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DOI：
10.1126/science.1188403
发表时间：
2010-06-04
期刊：
Science (New York, N.Y.)
影响因子：
--
作者：
Gustafson JL;Lim D;Miller SJ
通讯作者：
Miller SJ
影响因子：
16.6
作者：
Cresswell, Alexander J.;Eey, Stanley T. -C.;Denmark, Scott E.
通讯作者：
Denmark, Scott E.
DOI：
10.1073/pnas.1005296107
发表时间：
2010-11-30
影响因子：
11.1
作者：
Denmark, Scott E.;Burk, Matthew T.
通讯作者：
Burk, Matthew T.
影响因子：
15
作者：
BOTT, G;FIELD, LD;STERNHELL, S
通讯作者：
STERNHELL, S
影响因子：
5.2
作者：
Ashizawa, Tomoko;Tanaka, Saiko;Yamada, Tohru
通讯作者：
Yamada, Tohru