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超越旋光性：在全合成中，剩下的并不总是正确的。

Beyond optical rotation: what's left is not always right in total synthesis.

作者信息

Joyce Leo A, Nawrat Christopher C, Sherer Edward C, Biba Mirlinda, Brunskill Andrew, Martin Gary E, Cohen Ryan D, Davies Ian W

机构信息

Department of Process Research & Development , Merck & Co., Inc. , Rahway , NJ 07065 , USA . Email:

Department of Modeling and Informatics , Merck & Co., Inc. , Rahway , NJ 07065 , USA.

出版信息

Chem Sci. 2017 Oct 30;9(2):415-424. doi: 10.1039/c7sc04249c. eCollection 2018 Jan 14.

DOI:10.1039/c7sc04249c
PMID:29629112
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5868320/
Abstract

This work describes the application of vibrational (VCD) and electronic (ECD) circular dichroism spectroscopy to solve the longstanding debate around the absolute configuration of (+)-frondosin B (). The absolute configuration of (+)- could confidently be assigned as () using these spectroscopic techniques. The discrepancy in the optical rotation (OR) values obtained in previous studies can be attributed to an undetected minor impurity ( 7%) that arose unexpectedly in a key step late in the synthesis. Additionally, the conditions used in the final step of the previous reports for demethylation to form the natural product proceeded with significant loss of enantiopurity. The large OR measured for the impurity at its observed level, when compared to the small rotation for the less enantiopure natural product , led to a measured OR value for the synthetic material that had the opposite sign of the natural product.

摘要

本工作描述了振动圆二色光谱（VCD）和电子圆二色光谱（ECD）在解决围绕（+）-蕨叶霉素B（）绝对构型的长期争论中的应用。使用这些光谱技术，可以确定地将（+）-的绝对构型指定为（）。先前研究中获得的旋光值差异可归因于合成后期关键步骤中意外出现的未检测到的少量杂质（7%）。此外，先前报告中用于脱甲基形成天然产物的最后一步所使用的条件导致对映体纯度有显著损失。与对映体纯度较低的天然产物的小旋光度相比，杂质在其观察水平下测得的大旋光度导致合成材料的旋光测量值与天然产物的符号相反。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/f5ea4fd4c8ba/c7sc04249c-s8.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/194d20f29e15/c7sc04249c-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/ab9a01205efd/c7sc04249c-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/5784a1df14df/c7sc04249c-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/7ade809b4e85/c7sc04249c-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/9ba862198105/c7sc04249c-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/bdb14036e52b/c7sc04249c-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/c0bfad83c6db/c7sc04249c-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/2d6a47af99bf/c7sc04249c-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/4029148c96a9/c7sc04249c-s7.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/92d4/5868320/f5ea4fd4c8ba/c7sc04249c-s8.jpg

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