Synthesis of Optically Pure Helicene Metallocenes
Synthesis of Optically Pure Helicene Metallocenes
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DOI：
10.1002/anie.201611488
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发表时间：
2017-02-13
影响因子：
16.6
通讯作者：
Nozaki, Kyoko
中科院分区：
文献类型：
--
作者：
Akiyama, Midori;Nozaki, Kyoko
合成了两种不同结构的螺烯和一种由外消旋-9H-环戊二烯并[1，2-c：4，3-c ']二菲阴离子（s）配位的二茂铁，即骨架中心含有一个[7]螺烯的[7]螺烯：单螺烯螺烯1及其铁类似物1（Fe）和两个[7]螺烯的双螺烯2。从配体前体的外消旋混合物开始，以7：3的比例获得外消旋-2和内消旋-2。由于[7]螺烯具有高的外消旋化屏障，因此以其纯形式分离出络合物的对映体;它们显示出大的旋光度和强烈的圆二色性（CD）响应。
Two types of ruthenocenes and a ferrocene coordinated by rac-9H-cyclopenta[1,2-c:4,3-c']diphenanthrenyl anion(s), a [7]helicene with a cyclopentadienyl moiety at the center of its skeleton, were successfully synthesized: monohelicene ruthenocene 1 and its iron analogue 1(Fe) with one [7]helicene ligand bound to the central metal, and bis-helicene ruthenocene 2 with two [7]helicenes. Starting from a racemic mixture of the ligand precursor, rac-2 and meso-2 were obtained in a 7: 3 ratio. Since the [7]helicene has a high racemization barrier, enantiomers of the complexes were isolated in their pure forms; they showed large optical rotations and intense circular dichroism (CD) responses.