• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

立体定向多取代铜烯醇盐的对映选择性烯丙基烷基化反应：构建无环季碳立体中心的一种方法

Enantioselective allylic alkylation of stereodefined polysubstituted copper enolates as an entry to acyclic quaternary carbon stereocentres.

作者信息

Nairoukh Zackaria, Kumar Gunda G K S Narayana, Minko Yury, Marek Ilan

机构信息

The Mallat Family Laboratory of Organic Chemistry , Schulich Faculty of Chemistry and Lise Meitner-Minerva Center for Computational Quantum Chemistry , Technion-Israel Institute of Technology , Technion City , Haifa 32000 , Israel . Email:

出版信息

Chem Sci. 2017 Jan 1;8(1):627-630. doi: 10.1039/c6sc03036j. Epub 2016 Sep 15.

DOI:10.1039/c6sc03036j
PMID:28451210
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5358538/
Abstract

A sequence of regio- and stereoselective carbometalation followed by oxidation of ynamides leads to stereodefined fully substituted enolates that subsequently react with various functionalized allyl bromide reagents to provide the expected products possessing an enantiomerically pure quaternary carbon stereocentre in the α-position to the carbonyl group in excellent yields and enantiomeric ratios after cleavage of the oxazolidinone moiety. Three new bonds are formed in a single-pot operation.

摘要

一系列区域和立体选择性的碳金属化反应，随后对炔酰胺进行氧化，生成立体定向的全取代烯醇盐，这些烯醇盐随后与各种官能化的烯丙基溴试剂反应，在恶唑烷酮部分裂解后，以优异的产率和对映体比例提供预期的产物，该产物在羰基的α位具有对映体纯的季碳立体中心。在单锅操作中形成了三个新键。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/75ce86fbce6f/c6sc03036j-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/55a30f482e70/c6sc03036j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/a45b5125b1ad/c6sc03036j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/e505c9216e97/c6sc03036j-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/75ce86fbce6f/c6sc03036j-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/55a30f482e70/c6sc03036j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/a45b5125b1ad/c6sc03036j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/e505c9216e97/c6sc03036j-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/bcca/5358538/75ce86fbce6f/c6sc03036j-s4.jpg

相似文献

1
Enantioselective allylic alkylation of stereodefined polysubstituted copper enolates as an entry to acyclic quaternary carbon stereocentres.立体定向多取代铜烯醇盐的对映选择性烯丙基烷基化反应：构建无环季碳立体中心的一种方法
Chem Sci. 2017 Jan 1;8(1):627-630. doi: 10.1039/c6sc03036j. Epub 2016 Sep 15.
2
Regio- and Diastereoselective Carbometalation Reaction of Cyclopropenes.环丙烯的区域和立体选择性碳金属化反应。
Acc Chem Res. 2022 Oct 4;55(19):2848-2868. doi: 10.1021/acs.accounts.2c00424. Epub 2022 Sep 14.
3
Forming all-carbon quaternary stereogenic centres in acyclic systems from alkynes.在非循环体系中通过炔烃形成全碳季立体中心。
Nature. 2012 Oct 25;490(7421):522-6. doi: 10.1038/nature11569.
4
Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates.对映选择性构建非环季碳立体中心：全取代酰胺烯醇化物的钯催化脱羧烯丙基烷基化反应。
J Am Chem Soc. 2017 Jul 19;139(28):9615-9620. doi: 10.1021/jacs.7b04086. Epub 2017 Jul 7.
5
Stereodefined Acyclic Polysubstituted Silyl Ketene Aminals: Asymmetric Formation of Aldol Products with Quaternary Carbon Stereocenters.立体定义的非循环多取代硅基烯酮亚胺：具有季碳立体中心的 Aldol 产物的不对称形成。
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14393-7. doi: 10.1002/anie.201507209. Epub 2015 Oct 8.
6
Stereodefined acyclic trisubstituted metal enolates towards the asymmetric formation of quaternary carbon stereocentres.用于季碳立体中心不对称形成的立体定向非环状三取代金属烯醇盐。
Chem Commun (Camb). 2014 Oct 28;50(84):12597-611. doi: 10.1039/c4cc04391j.
7
Stereoselective Formation of Fully Substituted Ketone Enolates.立体选择性形成全取代酮烯醇盐。
Angew Chem Int Ed Engl. 2016 Apr 25;55(18):5517-20. doi: 10.1002/anie.201601883. Epub 2016 Mar 29.
8
Organocatalytic enantioselective allylic alkylation of α-aryl γ-lactones: an approach to densely functionalized quaternary stereocentres.有机催化的 α-芳基 γ-内酰胺的对映选择性烯丙基烷基化：一种构建高官能化的季立体中心的方法。
Chem Commun (Camb). 2020 Jun 18;56(49):6640-6643. doi: 10.1039/d0cc02058c.
9
Enantioselective Rhodium-Catalyzed Allylic Alkylation of Prochiral α,α-Disubstituted Aldehyde Enolates for the Construction of Acyclic Quaternary Stereogenic Centers.手性铑催化前手性 α,α-二取代醛烯醇化物的对映选择性烯丙基烷基化反应构建非环季碳手性中心。
J Am Chem Soc. 2016 Nov 30;138(47):15303-15306. doi: 10.1021/jacs.6b10099. Epub 2016 Nov 18.
10
Asymmetric synthesis of multiple quaternary stereocentre-containing cyclopentyls by oxazolidinone-promoted Nazarov cyclizations.通过恶唑烷酮促进的纳扎罗夫环化反应不对称合成含多个季碳立体中心的环戊基化合物
Chem Sci. 2018 Apr 20;9(20):4644-4649. doi: 10.1039/c8sc00031j. eCollection 2018 May 28.

引用本文的文献

1
Atom-economic and stereoselective catalytic synthesis of fully substituted enol esters/carbonates of amides in acyclic systems enabled by boron Lewis acid catalysis.硼路易斯酸催化实现非环状体系中酰胺的全取代烯醇酯/碳酸酯的原子经济性和立体选择性催化合成。
Chem Sci. 2023 Apr 26;14(21):5608-5618. doi: 10.1039/d3sc01394d. eCollection 2023 May 31.
2
Asymmetric synthesis with ynamides: unique reaction control, chemical diversity and applications.炔酰胺的不对称合成：独特的反应控制、化学多样性及应用。
Chem Soc Rev. 2020 Dec 7;49(23):8543-8583. doi: 10.1039/d0cs00769b. Epub 2020 Oct 19.
3
Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates.

本文引用的文献

1
The Catalytic Enantioselective Construction of Molecules with Quaternary Carbon Stereocenters.具有季碳立体中心的分子的催化对映选择性构建。
Angew Chem Int Ed Engl. 1998 Mar 2;37(4):388-401. doi: 10.1002/(SICI)1521-3773(19980302)37:4<388::AID-ANIE388>3.0.CO;2-V.
2
Stereoselective Formation of Fully Substituted Ketone Enolates.立体选择性形成全取代酮烯醇盐。
Angew Chem Int Ed Engl. 2016 Apr 25;55(18):5517-20. doi: 10.1002/anie.201601883. Epub 2016 Mar 29.
3
Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms.
手性催化非环季碳中心的合成：全取代非环烯醇碳酸酯的钯催化脱羧烯丙基烷基化反应。
J Am Chem Soc. 2018 Aug 15;140(32):10109-10112. doi: 10.1021/jacs.8b05560. Epub 2018 Aug 2.
4
Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates.对映选择性构建非环季碳立体中心：全取代酰胺烯醇化物的钯催化脱羧烯丙基烷基化反应。
J Am Chem Soc. 2017 Jul 19;139(28):9615-9620. doi: 10.1021/jacs.7b04086. Epub 2017 Jul 7.
含相邻手性季碳中心的天然产物的合成策略
Angew Chem Int Ed Engl. 2016 Mar 18;55(13):4156-86. doi: 10.1002/anie.201507549. Epub 2016 Feb 2.
4
Stereodefined Acyclic Polysubstituted Silyl Ketene Aminals: Asymmetric Formation of Aldol Products with Quaternary Carbon Stereocenters.立体定义的非循环多取代硅基烯酮亚胺：具有季碳立体中心的 Aldol 产物的不对称形成。
Angew Chem Int Ed Engl. 2015 Nov 23;54(48):14393-7. doi: 10.1002/anie.201507209. Epub 2015 Oct 8.
5
Enantioselective rhodium-catalyzed allylic substitution with a nitrile anion: construction of acyclic quaternary carbon stereogenic centers.手性铑催化的腈阴离子对烯丙位的不对称取代：构建非环季碳立体中心。
J Am Chem Soc. 2015 May 20;137(19):6156-9. doi: 10.1021/jacs.5b02810. Epub 2015 May 5.
6
Stereocontrolled Formation of Several Carbon-Carbon Bonds in Acyclic Systems.无环体系中几个碳-碳键的立体控制形成
Chem Rev. 2015 Sep 9;115(17):9175-206. doi: 10.1021/cr500715t. Epub 2015 Mar 13.
7
Catalytic enantioselective synthesis of quaternary carbon stereocentres.季碳立体中心的催化对映选择性合成。
Nature. 2014 Dec 11;516(7530):181-91. doi: 10.1038/nature14007.
8
Stereoselective formation of quaternary stereogenic centers via alkylation of α-substituted malonate-imidazolidinones.通过α-取代丙二酸-咪唑烷酮的烷基化反应立体选择性地形成季碳立体中心。
J Org Chem. 2015 Jan 16;80(2):762-9. doi: 10.1021/jo502140d. Epub 2014 Dec 19.
9
Stereodefined acyclic trisubstituted metal enolates towards the asymmetric formation of quaternary carbon stereocentres.用于季碳立体中心不对称形成的立体定向非环状三取代金属烯醇盐。
Chem Commun (Camb). 2014 Oct 28;50(84):12597-611. doi: 10.1039/c4cc04391j.
10
The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis.钯催化不对称烯丙基烷基化反应在全合成中构建全碳季碳立体中心
European J Org Chem. 2013 May 1;2013(14):2745-2759. doi: 10.1002/ejoc.201201761.