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从邻位全钯化苯甘氨酸衍生物的羰基化反应合成构象受限的谷氨酸和谷氨酰胺衍生物。

Synthesis of conformationally restricted glutamate and glutamine derivatives from carbonylation of orthopalladated phenylglycine derivatives.

机构信息

Instituto de Síntesis Química y Catálisis Homogénea, CSIC - Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.

出版信息

Beilstein J Org Chem. 2012;8:1569-75. doi: 10.3762/bjoc.8.179. Epub 2012 Sep 18.

DOI:10.3762/bjoc.8.179
PMID:23209488
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3510988/
Abstract

A new method for the regioselective synthesis of 2-alkoxycarbonyl- and 2-(aminocarbonyl)phenylglycinate methyl esters has been developed. The reaction of the orthopalladated complex Pd(μ-Cl)(C(6)H(4)(CH(CO(2)Me)NMe(2))-2) (1) with nucleophiles HNu under a CO atmosphere results in the selective incorporation of the C(O)Nu moiety to the phenyl ring and formation of the carbonyl species ortho-C(6)H(4)(C(O)Nu)(CH(CO(2)Me)NMe(2)) (2a-j) (Nu = OR, NHR, NR(2)). Compounds 2a-j are conformationally restricted analogues of glutamic acid and glutamine and are interesting due to their biological and pharmacological properties. The reaction of Pd(μ-Cl)(C(6)H(4)(CH(CO(2)Me)NHTf)-2) (3) with nucleophiles in a CO atmosphere results, however, in the formation of the cyclic isoindolinone or the open 2-carboxyphenylglycine methyl esters, with the reaction outcome being driven by the choice of the solvent.

摘要

一种新的区域选择性合成 2-烷氧羰基-和 2-(氨甲酰基)苯甘氨酸甲酯的方法已经开发出来。邻钯配合物Pd(μ-Cl)(C(6)H(4)(CH(CO(2)Me)NMe(2))-2)（1）与亲核试剂 HNu 在 CO 气氛下反应，选择性地将 C(O)Nu 部分引入苯环并形成羰基化合物邻-C(6)H(4)(C(O)Nu)(CH(CO(2)Me)NMe(2))（2a-j）（Nu = OR、NHR、NR(2)）。化合物 2a-j 是谷氨酸和谷氨酰胺的构象限制类似物，由于其具有生物和药理学性质而引起关注。然而，Pd(μ-Cl)(C(6)H(4)(CH(CO(2)Me)NHTf)-2)（3）与亲核试剂在 CO 气氛下的反应导致环状异吲哚啉酮或开链 2-羧基苯甘氨酸甲酯的形成，反应结果取决于溶剂的选择。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/37501011f47a/Beilstein_J_Org_Chem-08-1569-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/ad78a4adefd9/Beilstein_J_Org_Chem-08-1569-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/f2f26478e8db/Beilstein_J_Org_Chem-08-1569-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/39892da6e4f8/Beilstein_J_Org_Chem-08-1569-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/782fc4021e3d/Beilstein_J_Org_Chem-08-1569-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/f138f570ab30/Beilstein_J_Org_Chem-08-1569-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/37501011f47a/Beilstein_J_Org_Chem-08-1569-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/ad78a4adefd9/Beilstein_J_Org_Chem-08-1569-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/f2f26478e8db/Beilstein_J_Org_Chem-08-1569-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/39892da6e4f8/Beilstein_J_Org_Chem-08-1569-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/782fc4021e3d/Beilstein_J_Org_Chem-08-1569-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/f138f570ab30/Beilstein_J_Org_Chem-08-1569-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7fa8/3510988/37501011f47a/Beilstein_J_Org_Chem-08-1569-g007.jpg

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J Am Chem Soc. 2012 Jun 20;134(24):9902-5. doi: 10.1021/ja3036459. Epub 2012 Jun 6.
2
Catalytic functionalization of unactivated primary C-H bonds directed by an alcohol.醇导向的未活化伯 C-H 键的催化官能化。
Nature. 2012 Feb 29;483(7387):70-3. doi: 10.1038/nature10785.
3
Atmospheric pressure aminocarbonylation of aryl iodides using palladium nanoparticles supported on MOF-5.
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Beilstein J Org Chem. 2018 Feb 27;14:523-530. doi: 10.3762/bjoc.14.38. eCollection 2018.
使用负载在 MOF-5 上的钯纳米粒子实现芳基碘代物的常压氨基羰基化反应。
Chem Commun (Camb). 2012 Feb 7;48(12):1805-7. doi: 10.1039/c2cc16808a.
4
Palladium-catalyzed carbon-monoxide-free aminocarbonylation of aryl halides using N-substituted formamides as an amide source.钯催化的芳基卤化物无一氧化碳氨基甲酰化反应，使用 N-取代甲酰胺作为酰胺源。
J Org Chem. 2011 Jul 1;76(13):5489-94. doi: 10.1021/jo200754v. Epub 2011 Jun 9.
5
Cross-dehydrogenative coupling reactions of sp3-hybridized C-H bonds.sp3杂化碳氢键的交叉脱氢偶联反应
Top Curr Chem. 2010;292:281-302. doi: 10.1007/128_2009_17.
6
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8
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