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复杂化学类型的光化学方法:在天然产物合成中的应用。

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis.

作者信息

Kärkäs Markus D, Porco John A, Stephenson Corey R J

机构信息

Department of Chemistry, University of Michigan , 930 North University Avenue, Ann Arbor, Michigan 48109, United States.

Department of Chemistry, Center for Molecular Discovery (BU-CMD), Boston University , 590 Commonwealth Avenue, Boston, Massachusetts 02215, United States.

出版信息

Chem Rev. 2016 Sep 14;116(17):9683-747. doi: 10.1021/acs.chemrev.5b00760. Epub 2016 Apr 27.

Abstract

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis.

摘要

光化学转化的应用是一种强大的策略,它能够在一步反应中从相对简单的构建模块形成高度复杂的分子结构。所有光促进转化的一个核心特征是在吸收光子后产生电子激发态。这会产生瞬态反应中间体,并显著改变化合物的反应活性。光提供的能量输入因此提供了一种手段来制备使用热方法无法组装的张力独特的目标化合物。本综述旨在强调光化学转化作为一种快速获得结构和立体化学多样骨架的工具。基于光化学转化的合成设计有潜力以令人印象深刻的效率提供复杂的多环碳骨架,这些骨架在全合成中具有很高的价值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/29a9/5025835/c42a7560dc2e/cr-2015-007602_0114.jpg

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