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Light on chirality

机译:手性轻

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摘要

Reactions that produce only one of two mirror-image forms of a molecule are a hot topic in organic synthesis. A light-driven catalyst provides good results, and the technique could be generally applicable. Chirality — the non-identity of a molecule with its mirror image — is ubiquitous. It occurs not only in biomolecules (amino acids, sugars, DNA and RNA are examples of chiral molecules), but also in man-made chemicals, materials and drugs. Catalytic asymmetric synthesis — the use of chiral catalysts to transfer and amplify chirality in chemical reactions — has therefore become a central topic in molecular science. Bach and colleagues (this issue, page 1139) now combine two approaches to asymmetric synthesis — the thermal and the photochemical— to control the spatial arrangement of the atoms in a chiial reaction product. The results could be seminal in the field of chiral photochemistry. In conventional thermal asymmetric synthesis, vibrational energy is supplied to a reaction in the presence of a chiral catalyst or enzyme. This activates ground-state reagent molecules to achieve an asymmetric transformation in which one of two enantiomers — mirror-image forms of a molecule — of a reaction product will be preferentially synthesized. The aim of photochemical asymmetric synthesis is the same, but its tools are different: it uses short-lived, weakly inter acting molecular states that have been excited not by heat but by absorbed light. This technique is more difficult to control than its thermal counterpart, and has therefore been less extensively studied, despite its inherent advantages — the low activation energy required for such reactions and the ability to create unstable molecules unique to photochemical reactions, for example.
机译:仅产生分子的两种镜像形式之一的反应是有机合成中的热门话题。光驱动的催化剂可提供良好的结果,该技术通常适用。手性是无处不在的,即具有镜像的分子的非同一性。它不仅存在于生物分子中(氨基酸,糖,DNA和RNA是手性分子的例子),而且还存在于人造化学物质,材料和药物中。因此,催化不对称合成-在化学反应中使用手性催化剂转移和放大手性-已成为分子科学的中心课题。 Bach及其同事(此问题,第1139页)现在结合了两种不对称合成方法-热和光化学-来控制手性反应产物中原子的空间排列。该结果在手性光化学领域可能具有开创性。在常规的热不对称合成中,在手性催化剂或酶的存在下将振动能提供给反应。这激活了基态试剂分子以实现不对称转化,其中将优先合成反应产物的两种对映异构体之一(分子的镜像形式)。光化学不对称合成的目的是相同的,但其工具却不同:它使用的是短暂的,弱相互作用的分子态,该分子态不是由热而是由吸收的光激发的。该技术比其热对应技术更难控制,因此尽管具有固有优势(例如,此类反应所需的活化能低,并且具有产生光化学反应所特有的不稳定分子的能力),但对它的研究较少。

著录项

  • 来源
    《Nature》 |2005年第7054期|p.1099-1100|共2页
  • 作者

    Yoshihisa Inoue;

  • 作者单位
  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 自然科学总论;
  • 关键词

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