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6-O-甲基-9(E)-羟基亚氨基红霉素A中螺缩酮的结构与构象分析

Structure and conformational analysis of spiroketals from 6-O-methyl-9(E)-hydroxyiminoerythronolide A.

作者信息

Čikoš Ana, Ćaleta Irena, Žiher Dinko, Vine Mark B, Elenkov Ivaylo J, Dukši Marko, Gembarovski Dubravka, Ilijaš Marina, Dragojević Snježana, Malnar Ivica, Alihodžić Sulejman

机构信息

GlaxoSmithKline Research Centre Zagreb Ltd, Prilaz baruna Filipovića 29, 10000 Zagreb, Croatia.

GlaxoSmithKline, New Frontiers Science Park, Harlow, CM19 5AW, United Kingdom.

出版信息

Beilstein J Org Chem. 2015 Aug 19;11:1447-57. doi: 10.3762/bjoc.11.157. eCollection 2015.

DOI:10.3762/bjoc.11.157
PMID:26425201
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4578343/
Abstract

Three novel spiroketals were prepared by a one-pot transformation of 6-O-methyl-9(E)-hydroxyiminoerythronolide A. We present the formation of a [4.5]spiroketal moiety within the macrolide lactone ring, but also the unexpected formation of a 10-C=11-C double bond and spontaneous change of stereochemistry at position 8-C. As a result, a thermodynamically stable structure was obtained. The structures of two new diastereomeric, unsaturated spiroketals, their configurations and conformations, were determined by means of NMR spectroscopy and molecular modelling. The reaction kinetics and mechanistic aspects of this transformation are discussed. These rearrangements provide a facile synthesis of novel macrolide scaffolds.

摘要

通过6-O-甲基-9（E）-羟基亚氨基红霉素A的一锅法转化制备了三种新型螺环缩酮。我们展示了在大环内酯内酯环内形成[4.5]螺环缩酮部分，同时还意外地形成了10-C=11-C双键以及8-C位立体化学的自发变化。结果，获得了一种热力学稳定的结构。通过核磁共振光谱和分子建模确定了两种新的非对映体不饱和螺环缩酮的结构、构型和构象。讨论了这种转化的反应动力学和机理方面。这些重排为新型大环内酯支架提供了简便的合成方法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/ba3ab0e0917e/Beilstein_J_Org_Chem-11-1447-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/30899b5713a6/Beilstein_J_Org_Chem-11-1447-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/379886614355/Beilstein_J_Org_Chem-11-1447-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/8e01a45e2447/Beilstein_J_Org_Chem-11-1447-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/67c65ca7a14c/Beilstein_J_Org_Chem-11-1447-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/aac5e54712d6/Beilstein_J_Org_Chem-11-1447-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/7171f0f16fd0/Beilstein_J_Org_Chem-11-1447-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/75fff8210d7a/Beilstein_J_Org_Chem-11-1447-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/31b25a481d82/Beilstein_J_Org_Chem-11-1447-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/ba3ab0e0917e/Beilstein_J_Org_Chem-11-1447-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/30899b5713a6/Beilstein_J_Org_Chem-11-1447-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/379886614355/Beilstein_J_Org_Chem-11-1447-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/8e01a45e2447/Beilstein_J_Org_Chem-11-1447-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/67c65ca7a14c/Beilstein_J_Org_Chem-11-1447-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/aac5e54712d6/Beilstein_J_Org_Chem-11-1447-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/7171f0f16fd0/Beilstein_J_Org_Chem-11-1447-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/75fff8210d7a/Beilstein_J_Org_Chem-11-1447-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/31b25a481d82/Beilstein_J_Org_Chem-11-1447-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7df6/4578343/ba3ab0e0917e/Beilstein_J_Org_Chem-11-1447-g010.jpg

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