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通过催化立体选择性闭环复分解反应制备大环Z-烯酸酯和（E，Z）-或（Z，E）-二烯酸酯。

Preparation of macrocyclic Z-enoates and (E,Z)- or (Z,E)-dienoates through catalytic stereoselective ring-closing metathesis.

作者信息

Zhang Hanmo, Yu Elsie C, Torker Sebastian, Schrock Richard R, Hoveyda Amir H

机构信息

Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.

出版信息

J Am Chem Soc. 2014 Nov 26;136(47):16493-6. doi: 10.1021/ja510768c. Epub 2014 Nov 17.

DOI:10.1021/ja510768c
PMID:25402822
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4270125/
Abstract

The first examples of catalyst-controlled stereoselective macrocyclic ring-closing metathesis reactions that generate Z-enoates as well as (E,Z)- or (Z,E)-dienoates are disclosed. Reactions promoted by 3.0-10 mol % of a Mo-based monoaryloxide pyrrolide complex proceed to completion within 2-6 h at room temperature. The desired macrocycles are formed in 79:21 to >98:2 Z/E selectivity; stereoisomerically pure products can be obtained in 43-75% yield after chromatography. Utility is demonstrated by application to a concise formal synthesis of the natural product (+)-aspicilin.

摘要

首次公开了通过催化剂控制的立体选择性大环闭环复分解反应生成Z-烯酸酯以及（E，Z）-或（Z，E）-二烯酸酯的实例。由3.0-10 mol%的钼基单芳氧基吡咯化物络合物促进的反应在室温下2-6小时内完成。所需的大环以79:21至>98:2的Z/E选择性形成；经色谱分离后，可获得产率为43-75%的立体异构纯产物。通过应用于天然产物（+）-阿斯匹林的简洁形式合成证明了其实用性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/55db86331917/ja-2014-10768c_0001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/55db86331917/ja-2014-10768c_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/f827494c0656/ja-2014-10768c_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/5ce314adf877/ja-2014-10768c_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/cd1c68661759/ja-2014-10768c_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/acb5d62ea400/ja-2014-10768c_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/4e98a6aefe0d/ja-2014-10768c_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/47c3/4277761/55db86331917/ja-2014-10768c_0001.jpg

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