A new model of light-powered chiral molecular motor with higher speed of rotation, part 1 - Synthesis and absolute stereostructure
A new model of light-powered chiral molecular motor with higher speed of rotation, part 1 - Synthesis and absolute stereostructure
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DOI：
10.1002/ejoc.200500322
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发表时间：
2005-10-28
影响因子：
2.8
通讯作者：
Harada, N
中科院分区：
文献类型：
--
作者：
Fujita, T;Kuwahara, S;Harada, N
为了开发具有更高转速的分子马达，设计了一种新型的五元环型光动力手性分子马达2，并首次以酮(+)-8为原料，以对映体形式直接合成了马达旋转异构体(-)-2a和(-)-2c。用樟脑磺酰胺-二氯邻苯二甲酸(CSDP酸；3)法对前体醇9和10进行了拆分，并通过对CSDP酯(-)-11b的X-射线晶体分析和化学关联确定了它们的绝对构型。由(1S，2S)-(+)-9或(1R，2S)-(-)-10生成的对映光酮(S)-(+)-8与TiCl3/LiAlH4发生McMurry反应，得到马达旋转异构体[Cd(-)257.8]-(2S，2‘S)-(M，M)-(E)-(-)-2a和[Cd(-)270.0]-(2S，2’S)-(M，M)-(Z)-2c。这些研究使我们能够毫不含糊地确定马达2的绝对立体结构，这对于控制马达旋转的方向至关重要。(C)Wiley-VCH Verlag GmbH&Co，KGaA，69451，德国温海姆，2005年)。
To develop a molecular motor with a higher speed of rotation, a new model light-powered chiral molecular motor 2 of five-membered ring type was designed, and the motor rotation isomers (-)-2a and (-)-2c were directly synthesized in enantiopure forms for the first time from the ketone (+)-8. The precursor alcohols 9 and 10 were enantioresolved by the camphorsultam-dichlorophthalic acid (CSDP acid; 3) method, and their absolute configurations were determined by X-ray crystallographic analysis of the CSDP ester (-)-11b and chemical correlations. The enantiopure ketone (S)-(+)-8 formed from (1S,2S)-(+)-9 or (1R,2S)-(-)-10 was subjected to the McMurry reaction with TiCl3/LiAlH4, yielding the motor rotation isomers [CD(-)257.8]-(2S,2'S)-(M,M)-(E)-(-)-2a and [CD(-)270.0]-(2S,2'S)-(M,M)-(Z)-(-)-2c. These studies enabled us unambiguously to determine the absolute stereostructure of the motor 2, which is of critical importance for control over the direction of motor rotation. ((c) Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2005).