• 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

通过无环前体的汇聚偶联合成角取代的反式稠合氢化茚。

Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.

作者信息

Jeso Valer, Aquino Claudio, Cheng Xiayun, Mizoguchi Haruki, Nakashige Mika, Micalizio Glenn C

机构信息

Department of Chemistry, Burke Laboratory, Dartmouth College , Hanover, New Hampshire 03755, United States.

出版信息

J Am Chem Soc. 2014 Jun 11;136(23):8209-12. doi: 10.1021/ja504374j. Epub 2014 May 29.

DOI:10.1021/ja504374j
PMID:24856045
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4063191/
Abstract

Angularly substituted trans-fused hydroindanes are now accessible by the direct and convergent union of trimethylsilyl (TMS)-alkynes with 4-hydroxy-1,6-enynes by a process that forges three C-C bonds, one C-H bond, and two new stereocenters. The annulation is proposed to proceed by initial formation of a Ti-alkyne complex (with a TMS-alkyne) followed by regioselective alkoxide-directed coupling with the enyne, stereoselective intramolecular cycloaddition, elimination of phenoxide, 1,3-metallotropic shift, and stereoselective protonation of the penultimate allylic organometallic intermediate. Several examples are given to demonstrate the compatibility of this reaction with substrates bearing aromatic and aliphatic substituents, and an empirical model is presented to accompany the stereochemical observations.

摘要

通过三甲基硅基（TMS）-炔烃与4-羟基-1,6-烯炔的直接和汇聚式结合，现在可以合成角取代的反式稠合氢化茚，该过程能形成三个C-C键、一个C-H键和两个新的立体中心。据推测，环化反应首先通过形成钛-炔烃络合物（与TMS-炔烃）进行，随后是区域选择性的醇盐导向的与烯炔的偶联、立体选择性的分子内环加成、酚盐的消除、1,3-金属迁移以及倒数第二个烯丙基有机金属中间体的立体选择性质子化。给出了几个例子来说明该反应与带有芳香族和脂肪族取代基的底物的兼容性，并提出了一个经验模型来配合立体化学观察结果。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/d8d8e8e35d63/ja-2014-04374j_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/76ee55221af8/ja-2014-04374j_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/1b2739b78e4a/ja-2014-04374j_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/b4cd328227d4/ja-2014-04374j_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/45cfe00cd932/ja-2014-04374j_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/4e4d0a7d77af/ja-2014-04374j_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/266e8c781523/ja-2014-04374j_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/d8d8e8e35d63/ja-2014-04374j_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/76ee55221af8/ja-2014-04374j_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/1b2739b78e4a/ja-2014-04374j_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/b4cd328227d4/ja-2014-04374j_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/45cfe00cd932/ja-2014-04374j_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/4e4d0a7d77af/ja-2014-04374j_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/266e8c781523/ja-2014-04374j_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/803d/4063191/d8d8e8e35d63/ja-2014-04374j_0007.jpg

相似文献

1
Synthesis of angularly substituted trans-fused hydroindanes by convergent coupling of acyclic precursors.通过无环前体的汇聚偶联合成角取代的反式稠合氢化茚。
J Am Chem Soc. 2014 Jun 11;136(23):8209-12. doi: 10.1021/ja504374j. Epub 2014 May 29.
2
Synthesis of Angularly Substituted trans-Fused Decalins through a Metallacycle-Mediated Annulative Cross-Coupling Cascade.通过金属环介导的稠合环化交叉偶联级联反应合成角取代的反式稠合十氢化萘。
Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13099-13103. doi: 10.1002/anie.201606962.
3
Synthesis of Highly Functionalized Decalins via Metallacycle-Mediated Cross-Coupling.通过金属环介导的交叉偶联合成高度官能化的十氢化萘。
J Am Chem Soc. 2015 May 27;137(20):6624-8. doi: 10.1021/jacs.5b02107. Epub 2015 May 12.
4
An annulation reaction for the synthesis of cross-conjugated triene-containing hydroindanes from acyclic precursors.一种由无环前体合成含交叉共轭三烯氢化茚的环化反应。
Org Lett. 2014 Oct 3;16(19):5144-7. doi: 10.1021/ol502496d. Epub 2014 Sep 12.
5
Asymmetric synthesis of dihydroindanes by convergent alkoxide-directed metallacycle-mediated bond formation.通过会聚的烷氧基导向的金属环介导的键形成进行二氢茚的不对称合成。
J Am Chem Soc. 2012 Feb 8;134(5):2766-74. doi: 10.1021/ja2105043. Epub 2012 Jan 31.
6
Synthesis of pyrrolidine derivatives by a platinum/brønsted acid relay catalytic cascade reaction.通过铂/布朗斯特酸接力催化串联反应合成吡咯烷衍生物
Chemistry. 2015 Feb 16;21(8):3409-14. doi: 10.1002/chem.201405776. Epub 2014 Dec 29.
7
Enantioselective synthesis of (-)-terpestacin and structural revision of siccanol using catalytic stereoselective fragment couplings and macrocyclizations.通过催化立体选择性片段偶联和大环化反应实现（-）-土荆霉素的对映选择性合成以及西卡诺醇的结构修正。
J Am Chem Soc. 2004 Sep 1;126(34):10682-91. doi: 10.1021/ja0470968.
8
Ligand-controlled enantioselective [2 + 2] cycloaddition of oxabicyclic alkenes with terminal alkynes using chiral iridium catalysts.手性铱催化剂控制的氧杂双环烯烃与末端炔烃的[2 + 2]环加成反应的对映选择性。
Org Lett. 2010 Jan 15;12(2):304-6. doi: 10.1021/ol902574c.
9
Synthetic studies on and mechanistic insight into [W(CO)5(L)]-catalyzed stereoselective construction of functionalized bicyclo[5.3.0]decane frameworks.[W(CO)5(L)]催化的官能化双环[5.3.0]癸烷骨架的立体选择性构建的合成研究及机理见解。
Chemistry. 2010 Sep 17;16(35):10785-96. doi: 10.1002/chem.201001003.
10
Enantioselective Type II Cycloaddition of Alkynes via C-C Activation of Cyclobutanones: Rapid and Asymmetric Construction of [3.3.1] Bridged Bicycles.通过环丁酮的 C-C 活化实现炔烃的对映选择性类型 II 环加成：[3.3.1]桥环型双环的快速和不对称构建。
J Am Chem Soc. 2020 Jul 29;142(30):13180-13189. doi: 10.1021/jacs.0c05647. Epub 2020 Jul 17.

引用本文的文献

1
Toward the Asymmetric Synthesis of Cardenolides and Related Steroidal Systems: -S2' of Organometallics with C14-C17 Vinylepoxides.朝着卡多内酯和相关甾体体系的不对称合成迈进：C14-C17 乙烯基环氧化物的金属有机试剂 -S2'。
Org Lett. 2022 Oct 7;24(39):7058-7061. doi: 10.1021/acs.orglett.2c02455. Epub 2022 Sep 26.
2
Progress toward the De Novo Asymmetric Synthesis of Euphanes.朝 euphanes 的从头不对称合成的进展。
Org Lett. 2022 May 27;24(20):3686-3690. doi: 10.1021/acs.orglett.2c01299. Epub 2022 May 18.
3
Stereoselective synthesis of pentasubstituted 1,3-dienes Ni-catalyzed reductive coupling of unsymmetrical internal alkynes.

本文引用的文献

1
Strategic redox relay enables a scalable synthesis of ouabagenin, a bioactive cardenolide.战略氧化还原接力使生物活性卡烯内酯哇巴因的可扩展合成成为可能。
Science. 2013 Jan 4;339(6115):59-63. doi: 10.1126/science.1230631.
2
Asymmetric synthesis of dihydroindanes by convergent alkoxide-directed metallacycle-mediated bond formation.通过会聚的烷氧基导向的金属环介导的键形成进行二氢茚的不对称合成。
J Am Chem Soc. 2012 Feb 8;134(5):2766-74. doi: 10.1021/ja2105043. Epub 2012 Jan 31.
3
A Diels-Alder Route to Angularly Functionalized Bicyclic Structures.
五取代1,3 - 二烯的立体选择性合成：镍催化的不对称内炔还原偶联反应
Chem Sci. 2020 Sep 10;11(37):10204-10211. doi: 10.1039/d0sc04173d.
4
Dative Directing Group Effects in Ti-Catalyzed [2+2+1] Pyrrole Synthesis: Chemo- and Regioselective Alkyne Heterocoupling.钛催化[2+2+1]吡咯合成中的给体导向基团效应：化学和区域选择性炔烃杂偶联
ACS Catal. 2019 Jan 4;9(1):216-223. doi: 10.1021/acscatal.8b04669. Epub 2018 Nov 29.
5
A Highly Chemo-, Regio-, and Stereoselective Metallacycle-Mediated Annulation Between a Conjugated Enyne and an Ene-Diyne.共轭烯炔与烯二炔之间通过金属环介导的高度化学、区域和立体选择性环化反应。
ARKIVOC. 2018;2018(4):132-138. doi: 10.24820/ark.5550190.p010.487. Epub 2018 Mar 28.
6
Modern applications of low-valent early transition metals in synthesis and catalysis.低价早期过渡金属在合成与催化中的现代应用。
Nat Rev Chem. 2019 Jan;3(1):15-34. doi: 10.1038/s41570-018-0059-x. Epub 2018 Nov 30.
7
Synthetic nat- or ent-steroids in as few as five chemical steps from epichlorohydrin.从表氯醇出发，通过少至五步化学反应即可合成天然或内源性甾体。
Nat Chem. 2018 Jan;10(1):70-77. doi: 10.1038/nchem.2865. Epub 2017 Sep 25.
8
Synthesis of Highly Oxygenated Carbocycles by Stereoselective Coupling of Alkynes to 1,3- and 1,4-Dicarbonyl Systems.通过炔烃对 1,3-和 1,4-二羰基化合物的立体选择性偶联合成高含氧碳环。
J Am Chem Soc. 2017 Sep 13;139(36):12374-12377. doi: 10.1021/jacs.7b06286. Epub 2017 Sep 1.
9
The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry.醇盐导向的金属环介导的环化交叉偶联化学的发展
Isr J Chem. 2017 Apr;57(3-4):228-238. doi: 10.1002/ijch.201600098. Epub 2016 Nov 9.
10
Metallacycle-Mediated Cross-Coupling in Natural Product Synthesis.金属环介导的交叉偶联反应在天然产物合成中的应用
Tetrahedron. 2016 Nov 10;72(45):7093-7123. doi: 10.1016/j.tet.2016.08.053. Epub 2016 Sep 7.
一条构建角功能化双环结构的狄尔斯-阿尔德路线。
Tetrahedron. 2010 Aug 1;66(33):6391-6398. doi: 10.1016/j.tet.2010.04.094.
4
Aliphatic imines in titanium-mediated reductive cross-coupling: unique reactivity of Ti(O-i-Pr)4/n-BuLi.钛介导的还原交叉偶联反应中的脂肪族亚胺：Ti(O-i-Pr)4/n-BuLi的独特反应性
Org Lett. 2009 Oct 15;11(20):4596-9. doi: 10.1021/ol901870n.
5
Improved dienophilicity of nitrocycloalkenes: prospects for the development of a trans-Diels-Alder paradigm.硝基环烯烃亲双烯体活性的提高：反式狄尔斯-阿尔德反应模式的发展前景
J Am Chem Soc. 2009 Sep 9;131(35):12576-8. doi: 10.1021/ja9058926.
6
Synthesis of (+)-cortistatin A.（+）-皮质抑素A的合成。
J Am Chem Soc. 2008 Jun 11;130(23):7241-3. doi: 10.1021/ja8023466. Epub 2008 May 14.
7
An alkoxide-directed carbometalation of internal alkynes.醇盐导向的内炔烃碳金属化反应。
J Am Chem Soc. 2006 Mar 8;128(9):2764-5. doi: 10.1021/ja057352w.
8
Cross-coupling reaction of thermally stable titanium(II)-alkyne complexes with aryl halides catalysed by a nickel complex.镍配合物催化热稳定的钛（II）-炔烃配合物与芳基卤化物的交叉偶联反应。
Chem Commun (Camb). 2003 Nov 21(22):2820-1. doi: 10.1039/b310565b.
9
Stereocontrolled Assembly of Cis or Trans Angularly Substituted Hydrindenes by the Unactivated Intramolecular Diels-Alder Reaction.通过未活化的分子内狄尔斯-阿尔德反应立体控制组装顺式或反式角取代氢化茚。
J Org Chem. 1996 Oct 18;61(21):7508-7512. doi: 10.1021/jo9610974.