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金催化3-烯-1-炔酰胺与异恶唑的[4+3]和[4+2]环化反应——3-氮杂庚三烯基阳离子新型6π电环化反应

Gold-catalyzed [4+3]- and [4+2]-annulations of 3-en-1-ynamides with isoxazoles novel 6π-electrocyclizations of 3-azahepta trienyl cations.

作者信息

Giri Sovan Sundar, Liu Rai-Shung

机构信息

Department of Chemistry , National Tsing-Hua University , Hsinchu , Taiwan , Republic of China . Email:

出版信息

Chem Sci. 2018 Feb 19;9(11):2991-2995. doi: 10.1039/c8sc00232k. eCollection 2018 Mar 21.

DOI:10.1039/c8sc00232k
PMID:29732082
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5915799/
Abstract

New gold-catalyzed [4+3]-annulations of 3-en-1-ynamides with isoxazoles afford 4-azepines efficiently; this process involves 6π electrocyclizations of gold-stabilized 3-azaheptatrienyl cations. In the presence of Zn(OTf), the resulting 4-azepines undergo skeletal rearrangement to furnish substituted pyridine derivatives. We subsequently develop new catalytic [4+2]-annulations between the same 3-en-1-ynamides and isoxazoles to deliver substituted pyridine products using Au(i)/Zn(ii) catalysts. This work reports the first success of the 6π electrocyclizations of heptatrienyl cations that are unprecedented in literature reports.

摘要

新型金催化的3-烯-1-炔酰胺与异恶唑的[4+3]环化反应能高效生成4-氮杂环庚三烯；该过程涉及金稳定的3-氮杂庚三烯基阳离子的6π电环化反应。在三氟甲磺酸锌（Zn(OTf)）存在下，生成的4-氮杂环庚三烯会发生骨架重排，得到取代吡啶衍生物。随后，我们开发了相同的3-烯-1-炔酰胺与异恶唑之间新的催化[4+2]环化反应，以使用金（I）/锌（II）催化剂来制备取代吡啶产物。这项工作报道了庚三烯基阳离子6π电环化反应的首次成功，这在文献报道中是前所未有的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/aac6d2a40856/c8sc00232k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/6af1dfe2045e/c8sc00232k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/785e85e3191c/c8sc00232k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/aac6d2a40856/c8sc00232k-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/6af1dfe2045e/c8sc00232k-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/785e85e3191c/c8sc00232k-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/58cf/5915799/aac6d2a40856/c8sc00232k-s3.jpg

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