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通过具有挑战性的闭环复分解反应合成含核糖的中环支架。

Synthesis of a Ribose-Incorporating Medium Ring Scaffold via a Challenging Ring-Closing Metathesis Reaction.

作者信息

Rankin Stuart S, Caldwell John J, Cronin Nora B, van Montfort Rob L M, Collins Ian

机构信息

Cancer Research UK Cancer Therapeutics Unit The Institute of Cancer Research SM2 5NG London United Kingdom.

Division of Structural Biology The Institute of Cancer Research SW7 3RP London United Kingdom.

出版信息

European J Org Chem. 2016 Sep;2016(26):4496-4507. doi: 10.1002/ejoc.201600756. Epub 2016 Aug 15.

DOI:10.1002/ejoc.201600756
PMID:28042283
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5157775/
Abstract

A practical synthesis of a novel oxabicyclo[6.2.1]undecenetriol useful as a medicinal chemistry scaffold has been developed starting from l-ribose. The sequence involves an oxidation/Grignard addition sequence and a challenging ring-closing metathesis (RCM) reaction as the ring forming step. Exploration of the RCM substrate protecting groups revealed the key factor for successful nine-membered medium ring formation to be conformational bias of the reacting alkenes of the RCM substrate by very bulky silyl ether protecting groups. The synthesis also allowed access to an epimeric triol and saturated and unsaturated variants of the nine-membered ring. The medium ring conformation of the oxabicyclo[6.2.1]undecenetriol was determined by X-ray crystallography and correlated to the solution state conformation by NMR experiments.

摘要

已开发出一种从 l-核糖出发实用的新型氧杂双环[6.2.1]十一碳三烯醇的合成方法，该化合物可用作药物化学骨架。该合成路线包括氧化/格氏加成步骤以及作为成环步骤的具有挑战性的关环复分解（RCM）反应。对 RCM 底物保护基的探索表明，通过非常庞大的甲硅烷基醚保护基使 RCM 底物的反应性烯烃具有构象偏向性是成功形成九元中环的关键因素。该合成方法还能够得到差向异构三醇以及九元环的饱和和不饱和变体。通过 X 射线晶体学确定了氧杂双环[6.2.1]十一碳三烯醇的中环构象，并通过 NMR 实验将其与溶液态构象相关联。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/3c0c991acb36/EJOC-2016-4496-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/5f19648497d5/EJOC-2016-4496-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/0a67b007a387/EJOC-2016-4496-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/104f15033b2a/EJOC-2016-4496-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/46d6977c776e/EJOC-2016-4496-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/9b2b399012cb/EJOC-2016-4496-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/a931a1b49577/EJOC-2016-4496-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/3c0c991acb36/EJOC-2016-4496-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/5f19648497d5/EJOC-2016-4496-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/0a67b007a387/EJOC-2016-4496-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/104f15033b2a/EJOC-2016-4496-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/46d6977c776e/EJOC-2016-4496-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/9b2b399012cb/EJOC-2016-4496-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/a931a1b49577/EJOC-2016-4496-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d9c/5157775/3c0c991acb36/EJOC-2016-4496-g002.jpg

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