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使用间接阳离子池法对环状酰亚胺离子进行立体选择性亲核加成反应：通过光谱构象分析和密度泛函理论计算阐明立体选择性

Stereoselective nucleophilic addition reactions to cyclic -acyliminium ions using the indirect cation pool method: Elucidation of stereoselectivity by spectroscopic conformational analysis and DFT calculations.

作者信息

Mitsudo Koichi, Yamamoto Junya, Akagi Tomoya, Yamashita Atsuhiro, Haisa Masahiro, Yoshioka Kazuki, Mandai Hiroki, Ueoka Koji, Hempel Christian, Yoshida Jun-Ichi, Suga Seiji

机构信息

Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan.

Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.

出版信息

Beilstein J Org Chem. 2018 May 24;14:1192-1202. doi: 10.3762/bjoc.14.100. eCollection 2018.

DOI:10.3762/bjoc.14.100
PMID:29977386
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6009180/
Abstract

In this study, six-membered -acyliminium ions were generated by the "indirect cation pool" method and reacted with several nucleophiles. These reactions afforded disubstituted piperidine derivatives with high diastereoselectivities and good to excellent yields. The conformations of the obtained -acyliminium ions were studied by low temperature NMR analyses and DFT calculations and were found to be consistent with the Steven's hypothesis.

摘要

在本研究中，通过“间接阳离子池”方法生成了六元酰亚胺离子，并使其与几种亲核试剂反应。这些反应以高非对映选择性和良好至优异的产率得到了二取代哌啶衍生物。通过低温核磁共振分析和密度泛函理论计算研究了所得酰亚胺离子的构象，发现其与史蒂文斯假说一致。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/c321574d0094/Beilstein_J_Org_Chem-14-1192-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/ce607c31d513/Beilstein_J_Org_Chem-14-1192-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/adf194670f81/Beilstein_J_Org_Chem-14-1192-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/10afc7a221ca/Beilstein_J_Org_Chem-14-1192-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/9b37a92cd0f4/Beilstein_J_Org_Chem-14-1192-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/852ccdcf2884/Beilstein_J_Org_Chem-14-1192-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/bdfee180e99d/Beilstein_J_Org_Chem-14-1192-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/4fac5b0f8e63/Beilstein_J_Org_Chem-14-1192-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/c321574d0094/Beilstein_J_Org_Chem-14-1192-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/ce607c31d513/Beilstein_J_Org_Chem-14-1192-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/adf194670f81/Beilstein_J_Org_Chem-14-1192-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/10afc7a221ca/Beilstein_J_Org_Chem-14-1192-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/9b37a92cd0f4/Beilstein_J_Org_Chem-14-1192-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/852ccdcf2884/Beilstein_J_Org_Chem-14-1192-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/bdfee180e99d/Beilstein_J_Org_Chem-14-1192-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/4fac5b0f8e63/Beilstein_J_Org_Chem-14-1192-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/1107/6009180/c321574d0094/Beilstein_J_Org_Chem-14-1192-g008.jpg

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