• 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

碘代立方烷与芳硫醇盐和二苯基膦负离子的光诱导亲核取代反应。实验与计算方法。

Photoinduced nucleophilic substitution of iodocubanes with arylthiolate and diphenylphosphanide ions. Experimental and computational approaches.

作者信息

Jimenez Liliana B, Puiatti Marcelo, Andrada Diego M, Brigante Federico, Crespo Andrada Karina F, Rossi Roberto A, Priefer Ronny, Pierini Adriana B

机构信息

INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria X5000HUA Córdoba Argentina

Krupp-Professur für Allgemeine und Anorganische Chemie, Universität des Saarlandes 66123 Saarbrücken Germany.

出版信息

RSC Adv. 2018 Nov 23;8(69):39222-39230. doi: 10.1039/c8ra06275g.

DOI:10.1039/c8ra06275g
PMID:35558007
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9090936/
Abstract

A new synthetic route to modify the cubane nucleus is reported here. Methyl-4-iodocubane-1-carboxylate (1) and 1,4-diiodocubane (2) were employed as reagents to react with arylthiolate and diphenylphosphanide ions under irradiation in liquid ammonia and dimethylsulphoxide. The reactions proceed to afford thioaryl- and diphenylphosphoryl- cubane derivatives in moderate to good yields. It is also found that the monosubstituted product with retention of the second iodine is an intermediate compound. Mechanistic aspects are supported by DFT calculations.

摘要

本文报道了一种修饰立方烷核的新合成路线。甲基 - 4 - 碘代立方烷 - 1 - 羧酸甲酯（1）和1,4 - 二碘代立方烷（2）用作试剂，在液氨和二甲亚砜中辐照下与芳硫醇盐和二苯基膦化物离子反应。反应进行得到硫芳基和二苯基磷酰基立方烷衍生物，产率适中至良好。还发现保留第二个碘的单取代产物是中间化合物。密度泛函理论计算支持了反应机理方面的研究。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/e1026cb93cfb/c8ra06275g-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/c4f4c577bc22/c8ra06275g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/9884f568371b/c8ra06275g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/8aab89321d77/c8ra06275g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/66eecfd983eb/c8ra06275g-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/b1c77c54380e/c8ra06275g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/e1026cb93cfb/c8ra06275g-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/c4f4c577bc22/c8ra06275g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/9884f568371b/c8ra06275g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/8aab89321d77/c8ra06275g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/66eecfd983eb/c8ra06275g-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/b1c77c54380e/c8ra06275g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c4f0/9090936/e1026cb93cfb/c8ra06275g-s5.jpg

相似文献

1
Photoinduced nucleophilic substitution of iodocubanes with arylthiolate and diphenylphosphanide ions. Experimental and computational approaches.碘代立方烷与芳硫醇盐和二苯基膦负离子的光诱导亲核取代反应。实验与计算方法。
RSC Adv. 2018 Nov 23;8(69):39222-39230. doi: 10.1039/c8ra06275g.
2
Reactions of diazines with nucleophiles--IV. The reactivity of 5-bromo-1,3,6-trimethyluracil with thiolate ions--substitution versus X-philic versus single electron transfer reactions.
Bioorg Med Chem. 1995 Jul;3(7):891-7. doi: 10.1016/0968-0896(95)00085-u.
3
Mechanistic insights on the cycloisomerization of polyunsaturated precursors catalyzed by platinum and gold complexes.铂和金配合物催化多不饱和前体环异构化的机理见解
Acc Chem Res. 2009 Aug 18;42(8):1026-36. doi: 10.1021/ar800200m.
4
Trends in alkyl substituent effects on nucleophilic reactions of carbonyl compounds: gas phase reactions between ammonia and R1R2COCH3+ oxonium ions.羰基化合物亲核反应中烷基取代基效应的趋势：氨与R1R2COCH3 + 氧鎓离子之间的气相反应
Org Biomol Chem. 2003 Feb 21;1(4):705-13. doi: 10.1039/b209955c.
5
Experimental and computational study of 6-exo and 7-endo cyclization of aryl radicals followed by tandem S(RN)1 substitution.芳基自由基 6-endo 和 7-exo 环化反应的实验和计算研究，随后进行串联 S(RN)1 取代反应。
J Org Chem. 2013 May 17;78(10):4719-29. doi: 10.1021/jo4001788. Epub 2013 May 2.
6
cine-Substitution reactions of metallabenzenes: an experimental and computational study.金属苯取代反应：实验与计算研究。
Chemistry. 2013 Aug 12;19(33):10982-91. doi: 10.1002/chem.201301398. Epub 2013 Jul 10.
7
Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization.大气压光电离中卤代苯掺杂剂与亲核试剂之间的亲核芳香取代反应
J Am Soc Mass Spectrom. 2016 Mar;27(3):422-31. doi: 10.1007/s13361-015-1315-7. Epub 2015 Dec 4.
8
The kinetics and mechanisms of aromatic nucleophilic substitution reactions in liquid ammonia.液氨中芳香亲核取代反应的动力学和机理。
J Org Chem. 2011 May 6;76(9):3286-95. doi: 10.1021/jo200170z. Epub 2011 Mar 31.
9
Organic reactivity in liquid ammonia.液氨中的有机反应性。
Org Biomol Chem. 2012 Aug 14;10(30):5732-9. doi: 10.1039/c2ob25064k. Epub 2012 Apr 26.
10
Rhodium(ii)-catalyzed annulation of N-sulfonyl-1,2,3-triazoles with 1,3,5-triazinanes to produce octahydro-1H-purine derivatives: a combined experimental and computational study.铑（II）催化N-磺酰基-1,2,3-三唑与1,3,5-三嗪烷环化反应制备八氢-1H-嘌呤衍生物：实验与计算相结合的研究
Chem Commun (Camb). 2019 May 28;55(43):6090-6093. doi: 10.1039/c9cc02294e. Epub 2019 May 9.

本文引用的文献

1
Cubane Cross-Coupling and Cubane-Porphyrin Arrays.立方烷交叉偶联与立方烷-卟啉阵列
Chemistry. 2018 Jan 24;24(5):1026-1030. doi: 10.1002/chem.201704344. Epub 2017 Nov 14.
2
Redox-Active Esters in Fe-Catalyzed C-C Coupling.铁催化的 C-C 偶联中的氧化还原活性酯。
J Am Chem Soc. 2016 Sep 7;138(35):11132-5. doi: 10.1021/jacs.6b07172. Epub 2016 Aug 29.
3
Cubane: 50 years later.立方烷：50年后。
Chem Rev. 2015 Jul 22;115(14):6719-45. doi: 10.1021/cr500523x. Epub 2015 Jun 23.
4
Cubanes in medicinal chemistry: synthesis of functionalized building blocks.药物化学中的立方烷：功能化结构单元的合成
Org Lett. 2014 Aug 15;16(16):4094-7. doi: 10.1021/ol501750k. Epub 2014 Jul 28.
5
Chloroform as a hydrogen atom donor in Barton reductive decarboxylation reactions.氯仿作为 Barton 还原脱羧反应中的氢原子供体。
J Org Chem. 2013 Jul 5;78(13):6677-87. doi: 10.1021/jo400927y. Epub 2013 Jun 24.
6
Experimental and computational study of 6-exo and 7-endo cyclization of aryl radicals followed by tandem S(RN)1 substitution.芳基自由基 6-endo 和 7-exo 环化反应的实验和计算研究，随后进行串联 S(RN)1 取代反应。
J Org Chem. 2013 May 17;78(10):4719-29. doi: 10.1021/jo4001788. Epub 2013 May 2.
7
Evaluation of a chiral cubane-based Schiff base ligand in asymmetric catalysis reactions.手性立方烷基席夫碱配体在不对称催化反应中的评价。
Beilstein J Org Chem. 2012;8:1814-8. doi: 10.3762/bjoc.8.207. Epub 2012 Oct 22.
8
Continuous surface charge polarizable continuum models of solvation. I. General formalism.溶剂化的连续表面电荷极化连续体模型。I. 一般形式。
J Chem Phys. 2010 Mar 21;132(11):114110. doi: 10.1063/1.3359469.
9
Inter- and intramolecular-bridge-mediated electron transfer in aliphatic halides.脂肪族卤化物中分子间和分子内桥介导的电子转移。
J Org Chem. 2006 Aug 18;71(17):6596-9. doi: 10.1021/jo060054c.
10
Accurate Coulomb-fitting basis sets for H to Rn.从氢到氡的精确库仑拟合基组。
Phys Chem Chem Phys. 2006 Mar 7;8(9):1057-65. doi: 10.1039/b515623h. Epub 2006 Jan 3.