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通过非对映异位基团选择实现局部去对称化:天然产物合成的一种赋能策略。

Local Desymmetrization through Diastereotopic Group Selection: An Enabling Strategy for Natural Product Synthesis.

作者信息

Horwitz Matthew A, Johnson Jeffrey S

机构信息

Department of Chemistry, The University of North Carolina at Chapel Hill Chapel Hill, NC 27599 (USA).

出版信息

European J Org Chem. 2017 Mar 17;2017(11):1381-1390. doi: 10.1002/ejoc.201601481. Epub 2017 Feb 7.

DOI:10.1002/ejoc.201601481
PMID:28533701
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5437555/
Abstract

The application of desymmetrization strategies in chemical synthesis has allowed fundamentally new synthetic sequences that efficiently create dense and polyfunctional stereochemical arrays. Enantiotopic group discrimination has become a well-established method of global desymmetrization, while the conceptually unique strategy of local desymmetrization by diastereotopic group discrimination has its own advantages. This microreview focuses on the application of local desymmetrization in natural product synthesis and places a particular emphasis on the efficiency engendered by diastereotopic group discrimination. Local desymmetrization is subdivided into three distinct manifolds; examples under each paradigm are presented and compared.

摘要

去对称化策略在化学合成中的应用使得全新的合成序列得以实现,这些序列能够高效地构建密集且多官能团的立体化学阵列。对映异位基团识别已成为一种成熟的全局去对称化方法,而通过非对映异位基团识别进行局部去对称化这一概念独特的策略也有其自身优势。本微型综述聚焦于局部去对称化在天然产物合成中的应用,并特别强调非对映异位基团识别所带来的效率提升。局部去对称化可细分为三种不同类型;每种类型下都给出了示例并进行了比较。

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本文引用的文献

1
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J Am Chem Soc. 2016 Nov 9;138(44):14789-14797. doi: 10.1021/jacs.6b09727. Epub 2016 Oct 27.
2
Organocatalytic enantioselective desymmetrisation.有机催化的对映选择性去对称化。
Chem Soc Rev. 2016 Oct 21;45(20):5474-5540. doi: 10.1039/c5cs00015g. Epub 2016 Jun 27.
3
Catalytic Enantioselective Desymmetrization Reactions to All-Carbon Quaternary Stereocenters.催化对映选择性去对称化反应构建全碳季碳手性中心。
Chem Rev. 2016 Jun 22;116(12):7330-96. doi: 10.1021/acs.chemrev.6b00094. Epub 2016 Jun 2.
4
Asymmetric Total Synthesis of the Indole Diterpene Alkaloid Paspaline.吲哚二萜生物碱帕斯巴灵的不对称全合成
J Org Chem. 2015 Oct 2;80(19):9740-66. doi: 10.1021/acs.joc.5b01844.
5
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7
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9
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10
Asymmetric synthesis of the aminocyclitol pactamycin, a universal translocation inhibitor.氨环醇 pactamycin 的不对称合成,一种通用易位抑制剂。
J Am Chem Soc. 2013 Nov 27;135(47):17990-8. doi: 10.1021/ja409944u. Epub 2013 Nov 18.