• 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

有机金属对映体骨架。连续的半频哪醇/1,5-“类迈克尔”反应作为构建桥头季碳中心氮杂[3.3.1]双环化合物的一种策略方法：应用于（-）-阿达林的全合成。

Organometallic enantiomeric scaffolding. Sequential semipinacol/1,5-"Michael-like" reactions as a strategic approach to bridgehead-quaternary center aza[3.3.1]bicyclics: application to the total synthesis of (-)-adaline.

作者信息

Coombs Thomas C, Zhang Yongqiang, Garnier-Amblard Ethel C, Liebeskind Lanny S

机构信息

Sanford S. Atwood Chemistry Center, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.

出版信息

J Am Chem Soc. 2009 Jan 28;131(3):876-7. doi: 10.1021/ja808533z.

DOI:10.1021/ja808533z
PMID:19123794
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2654255/
Abstract

A nontraditional approach to the enantiocontrolled construction of quaternary center-bearing heteroatom-bridged bicyclo[3.3.1]nonanes (homotropanes) is reported that is based on organometallic enantiomeric scaffolding. This strategy takes advantage of the unique reactivity profiles of TpMo(CO)(2)(5-oxo-eta(3)-pyranyl) and TpMo(CO)(2)(5-oxo-eta(3)-pyridinyl) scaffolds, and features a molybdenum-mediated semipinacol/1,5-"Michael-like" reaction sequence to establish the quaternary center and synthesize the bridged bicyclic structure. An asymmetric total synthesis of (-)-adaline highlights this methodology.

摘要

报道了一种基于有机金属对映体支架的非传统方法，用于对映体控制构建含季碳中心的杂原子桥连双环[3.3.1]壬烷（高托烷）。该策略利用了TpMo(CO)(2)(5-氧代-η(3)-吡喃基)和TpMo(CO)(2)(5-氧代-η(3)-吡啶基)支架独特的反应特性，并以钼介导的半频哪醇/1,5-“类迈克尔”反应序列来构建季碳中心并合成桥连双环结构。(-)-阿达林的不对称全合成突出了这种方法。

相似文献

1
Organometallic enantiomeric scaffolding. Sequential semipinacol/1,5-"Michael-like" reactions as a strategic approach to bridgehead-quaternary center aza[3.3.1]bicyclics: application to the total synthesis of (-)-adaline.有机金属对映体骨架。连续的半频哪醇/1,5-“类迈克尔”反应作为构建桥头季碳中心氮杂[3.3.1]双环化合物的一种策略方法：应用于（-）-阿达林的全合成。
J Am Chem Soc. 2009 Jan 28;131(3):876-7. doi: 10.1021/ja808533z.
2
Eta3-pyranyl and eta3-pyridinyl molybdenum pi-complexes as chiral scaffolds for the enantioselective construction of substituted oxa- and aza[3.3.1]bicyclics: first enantio- and regiocontrolled [5+3] cycloaddition reactions.η³-吡喃基和η³-吡啶基钼π-配合物作为用于对映选择性构建取代的氧杂和氮杂[3.3.1]双环化合物的手性骨架：首例对映和区域控制的[5+3]环加成反应
J Am Chem Soc. 2003 Jul 30;125(30):9026-7. doi: 10.1021/ja035424i.
3
Organometallic enantiomeric scaffolding: general access to 2-substituted oxa- and azabicyclo[3.2.1]octenes via a Brønsted acid catalyzed [5 + 2] cycloaddition reaction.有机金属对映体骨架：通过布朗斯特酸催化的[5 + 2]环加成反应通用合成2-取代的氧杂和氮杂双环[3.2.1]辛烯
J Am Chem Soc. 2008 Jun 11;130(23):7449-58. doi: 10.1021/ja800664v. Epub 2008 May 15.
4
A new reaction motif: "homo-S(N)2'-like" direct nucleophilic addition to neutral eta(3)-allylmolybdenum complexes. total synthesis of the antimalarial (+)-isofebrifugine.一种新的反应模式：“类同-S(N)2'”直接亲核加成到中性η(3)-烯丙基钼配合物。抗疟药物(+)-异非布立定的全合成。
J Am Chem Soc. 2009 Sep 9;131(35):12546-7. doi: 10.1021/ja9056322.
5
Practical, scalable, high-throughput approaches to eta3-pyranyl and eta3-pyridinyl organometallic enantiomeric scaffolds using the Achmatowicz reaction.使用阿赫马托维茨反应制备η³-吡喃基和η³-吡啶基有机金属对映体支架的实用、可扩展、高通量方法。
J Org Chem. 2008 Feb 1;73(3):882-8. doi: 10.1021/jo702006z. Epub 2008 Jan 3.
6
Aza-Quaternary Scaffolds from Selective Bond Cleavage of Bridgehead-Substituted 7-Azabicyclo[2.2.1]heptane: Total Synthesis of (+)-Cylindricines C-E and (-)-Lepadiformine A.通过桥头取代的7-氮杂双环[2.2.1]庚烷的选择性键裂解制备氮杂季碳骨架：（+）-圆柱海绵素C-E和（-）-柄海鞘素A的全合成
Chemistry. 2015 Sep 7;21(37):13120-6. doi: 10.1002/chem.201501859. Epub 2015 Jul 28.
7
Stereoselective synthesis of (+)-euphococcinine and (-)-adaline.（+）-喜树球宁和（-）-阿达林的立体选择性合成。
J Org Chem. 2009 May 15;74(10):3806-14. doi: 10.1021/jo9001992.
8
Organometallic enantiomeric scaffolding. A molybdenum-mediated intramolecular nucleophilic ketalization-demetalation cascade. Total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin.有机金属对映体支架。钼介导的分子内亲核缩酮化-脱金属化级联反应。(+)-(1R,2S,5S,7R)-2-羟基外向-短叶松素的全合成。
Org Lett. 2009 Aug 20;11(16):3682-5. doi: 10.1021/ol901523g.
9
Organometallic enantiomeric scaffolding: a strategy for the enantiocontrolled construction of regio- and stereodivergent trisubstituted piperidines from a common precursor.金属有机手性骨架：一种从共同前体制备区域和立体发散的三取代吗啉的对映选择性构建的策略。
J Am Chem Soc. 2011 May 18;133(19):7517-27. doi: 10.1021/ja201012p. Epub 2011 Apr 22.
10
Asymmetric construction of quaternary centers by enantioselective allylation: application to the synthesis of the serotonin antagonist LY426965.
Org Lett. 2002 May 30;4(11):1951-3. doi: 10.1021/ol025971t.

引用本文的文献

1
Asymmetric total synthesis strategies of halichlorine and pinnaic acid.卤氯灵和海石竹酸的不对称全合成策略。
RSC Adv. 2023 Nov 17;13(48):33754-33769. doi: 10.1039/d3ra06955a. eCollection 2023 Nov 16.
2
Different routes for the construction of biologically active diversely functionalized bicyclo[3.3.1]nonanes: an exploration of new perspectives for anticancer chemotherapeutics.构建具有生物活性的多种功能化双环[3.3.1]壬烷的不同途径：抗癌化疗新视角探索
RSC Adv. 2023 Jul 25;13(32):22389-22480. doi: 10.1039/d3ra02003g. eCollection 2023 Jul 19.
3
Recent progress in the synthesis of homotropane alkaloids adaline, euphococcinine and -methyleuphococcinine.降托烷生物碱阿达林、喜树柯宁碱和甲基喜树柯宁碱合成的最新进展。
Beilstein J Org Chem. 2021 Jan 5;17:28-41. doi: 10.3762/bjoc.17.4. eCollection 2021.
4
Organometallic enantiomeric scaffolding: a strategy for the enantiocontrolled construction of regio- and stereodivergent trisubstituted piperidines from a common precursor.金属有机手性骨架：一种从共同前体制备区域和立体发散的三取代吗啉的对映选择性构建的策略。
J Am Chem Soc. 2011 May 18;133(19):7517-27. doi: 10.1021/ja201012p. Epub 2011 Apr 22.
5
Novel Substitutions of 1-Alkoxy- and 1-Arylsulfonyloxy-η-Allylmolybdenum Complexes. A Case for η-Alkenyl Carbene Complexes as Intermediates.1-烷氧基-和1-芳基磺酰氧基-η-烯丙基钼配合物的新型取代反应。以η-烯基卡宾配合物作为中间体的实例。
Organometallics. 2010 Nov 8;29(21):5083-5097. doi: 10.1021/om100305f.
6
A new reaction motif: "homo-S(N)2'-like" direct nucleophilic addition to neutral eta(3)-allylmolybdenum complexes. total synthesis of the antimalarial (+)-isofebrifugine.一种新的反应模式：“类同-S(N)2'”直接亲核加成到中性η(3)-烯丙基钼配合物。抗疟药物(+)-异非布立定的全合成。
J Am Chem Soc. 2009 Sep 9;131(35):12546-7. doi: 10.1021/ja9056322.
7
Organometallic enantiomeric scaffolding. A molybdenum-mediated intramolecular nucleophilic ketalization-demetalation cascade. Total synthesis of (+)-(1R,2S,5S,7R)-2-hydroxy-exo-brevicomin.有机金属对映体支架。钼介导的分子内亲核缩酮化-脱金属化级联反应。(+)-(1R,2S,5S,7R)-2-羟基外向-短叶松素的全合成。
Org Lett. 2009 Aug 20;11(16):3682-5. doi: 10.1021/ol901523g.

本文引用的文献

1
Organometallic enantiomeric scaffolding: general access to 2-substituted oxa- and azabicyclo[3.2.1]octenes via a Brønsted acid catalyzed [5 + 2] cycloaddition reaction.有机金属对映体骨架：通过布朗斯特酸催化的[5 + 2]环加成反应通用合成2-取代的氧杂和氮杂双环[3.2.1]辛烯
J Am Chem Soc. 2008 Jun 11;130(23):7449-58. doi: 10.1021/ja800664v. Epub 2008 May 15.
2
Practical, scalable, high-throughput approaches to eta3-pyranyl and eta3-pyridinyl organometallic enantiomeric scaffolds using the Achmatowicz reaction.使用阿赫马托维茨反应制备η³-吡喃基和η³-吡啶基有机金属对映体支架的实用、可扩展、高通量方法。
J Org Chem. 2008 Feb 1;73(3):882-8. doi: 10.1021/jo702006z. Epub 2008 Jan 3.
3
The enantiomeric scaffold approach to highly functionalized 1-oxadecalines: enantio- and regiocontrolled [4 + 2] cycloadditions of 5-alkenyl-eta3-pyranylmolybdenum complexes.用于高官能化1-氧杂萘满的对映体支架方法：5-烯基-η3-吡喃钼配合物的对映和区域控制的[4 + 2]环加成反应
J Am Chem Soc. 2007 Feb 14;129(6):1816-25. doi: 10.1021/ja067104f.
4
Organometallic enantiomeric scaffolding: organometallic chirons. Total synthesis of (-)-Bao Gong Teng A by a molybdenum-mediated [5 + 2] cycloaddition.有机金属对映体支架：有机金属手性子。通过钼介导的[5 + 2]环加成全合成(-)-包公藤A。
J Am Chem Soc. 2006 Jan 18;128(2):465-72. doi: 10.1021/ja055623x.
5
Synthesis of substituted oxa- and aza[3.2.1] and [4.3.1]bicyclics via an unprecedented molybdenum-mediated 1,5-"Michael-type" reaction.通过前所未有的钼介导的1,5-“迈克尔型”反应合成取代的氧杂和氮杂[3.2.1]及[4.3.1]双环化合物。
J Am Chem Soc. 2005 Aug 17;127(32):11258-9. doi: 10.1021/ja0538132.
6
Eta3-pyranyl and eta3-pyridinyl molybdenum pi-complexes as chiral scaffolds for the enantioselective construction of substituted oxa- and aza[3.3.1]bicyclics: first enantio- and regiocontrolled [5+3] cycloaddition reactions.η³-吡喃基和η³-吡啶基钼π-配合物作为用于对映选择性构建取代的氧杂和氮杂[3.3.1]双环化合物的手性骨架：首例对映和区域控制的[5+3]环加成反应
J Am Chem Soc. 2003 Jul 30;125(30):9026-7. doi: 10.1021/ja035424i.
7
Contiguous stereogenic quaternary carbons: a daunting challenge in natural products synthesis.相邻的手性季碳：天然产物合成中的一项艰巨挑战。
Proc Natl Acad Sci U S A. 2004 Aug 17;101(33):11943-8. doi: 10.1073/pnas.0402416101. Epub 2004 Jul 1.
8
Catalytic asymmetric synthesis of all-carbon quaternary stereocenters.全碳季碳立体中心的催化不对称合成。
Proc Natl Acad Sci U S A. 2004 Apr 13;101(15):5363-7. doi: 10.1073/pnas.0307113101. Epub 2004 Jan 14.
9
Enantiocontrolled synthesis of 2,6-disubstituted piperidines by desymmetrization of meso-eta-(3,4,5)-dihydropyridinylmolybdenum complexes. application to the total synthesis of (-)-dihydropinidine and (-)-andrachcinidine.通过内消旋-η-(3,4,5)-二氢吡啶基钼配合物的去对称化对映选择性合成2,6-二取代哌啶。应用于(-)-二氢哌啶和(-)-山油柑碱的全合成。
J Am Chem Soc. 2003 Mar 12;125(10):2878-9. doi: 10.1021/ja029537y.
10
New oxidative demetalation protocol for molybdenum pi-complexes: enantiocontrolled synthesis of unsaturated ketones and lactones.钼π配合物的新型氧化脱金属反应方案：对映体控制合成不饱和酮和内酯
J Org Chem. 2002 Aug 9;67(16):5773-8. doi: 10.1021/jo020002x.