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新型镍氨基苯酚配合物的合成与反应活性

Synthesis and reactivity of new aminophenolate complexes of nickel.

作者信息

Yu Siqi, Wang Huan, Sledziewski Jill E, Madhira Venkata N, Takahashi Cyrus G, Leon Michelle K, Dudkina Yulia B, Budnikova Yulia H, Vicic David A

机构信息

Department of Chemistry, Lehigh University, 6 E. Packer Ave., Bethlehem, PA 18015, USA.

Department of Chemistry, University of Hawaii, 2545 McCarthy Mall, Honolulu, HI 96822, USA.

出版信息

Molecules. 2014 Sep 2;19(9):13603-13. doi: 10.3390/molecules190913603.

DOI:10.3390/molecules190913603
PMID:25185067
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6271139/
Abstract

New well-defined, paramagnetic nickel complexes have been prepared and characterized by X-ray crystallography. The complexes were found to be active for the cross-coupling of alkyl electrophiles (especially ethyl 2-bromobutyrate) with alkyl Grignard reagents. The ligand architecture in these new complexes could potentially be rendered chiral, opening up future possibilities for performing asymmetric cross-coupling reactions.

摘要

新型结构明确的顺磁性镍配合物已被制备出来,并通过X射线晶体学进行了表征。发现这些配合物对于烷基亲电试剂(特别是2-溴丁酸乙酯)与烷基格氏试剂的交叉偶联反应具有活性。这些新型配合物中的配体结构有可能被转化为手性结构,为进行不对称交叉偶联反应开辟了未来的可能性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/706c695d6eef/molecules-19-13603-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/0ac3f499ef70/molecules-19-13603-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/9c29753a3106/molecules-19-13603-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/0450b773dd33/molecules-19-13603-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/3aa387f26627/molecules-19-13603-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/73b6cc8c3918/molecules-19-13603-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/ce43f95eebf2/molecules-19-13603-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/58cc9832e743/molecules-19-13603-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/706c695d6eef/molecules-19-13603-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/0ac3f499ef70/molecules-19-13603-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/9c29753a3106/molecules-19-13603-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/0450b773dd33/molecules-19-13603-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/3aa387f26627/molecules-19-13603-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/73b6cc8c3918/molecules-19-13603-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/ce43f95eebf2/molecules-19-13603-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/58cc9832e743/molecules-19-13603-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6dba/6271139/706c695d6eef/molecules-19-13603-g004.jpg

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本文引用的文献

1
Cross-electrophile coupling: principles of reactivity and selectivity.交叉亲电偶联:反应性与选择性原理
J Org Chem. 2014 Jun 6;79(11):4793-8. doi: 10.1021/jo500507s. Epub 2014 May 15.
2
Nickel/bis(oxazoline)-catalyzed asymmetric Negishi arylations of racemic secondary benzylic electrophiles to generate enantioenriched 1,1-diarylalkanes.镍/双(恶唑啉)催化外消旋仲苄基亲电试剂的不对称根岸芳基化反应,生成对映体富集的1,1-二芳基烷烃。
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3
Mechanism and selectivity in nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides.
镍催化芳基卤化物与烷基卤化物的交叉电子亲核偶联反应的机理和选择性。
J Am Chem Soc. 2013 Oct 30;135(43):16192-7. doi: 10.1021/ja407589e. Epub 2013 Oct 21.
4
Bimetallic oxidative addition involving radical intermediates in nickel-catalyzed alkyl-alkyl Kumada coupling reactions.镍催化的烷基-烷基 Kumada 偶联反应中涉及自由基中间体的双金属氧化加成。
J Am Chem Soc. 2013 Aug 14;135(32):12004-12. doi: 10.1021/ja4051923. Epub 2013 Aug 1.
5
Nickel-mediated oxidative fluorination for PET with aqueous [18F] fluoride.镍介导的氧化氟化作用用于含有水性 [18F] 氟化物的正电子发射断层扫描技术(PET)。
J Am Chem Soc. 2012 Oct 24;134(42):17456-8. doi: 10.1021/ja3084797. Epub 2012 Oct 12.
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Catalytic enantioselective cross-couplings of secondary alkyl electrophiles with secondary alkylmetal nucleophiles: Negishi reactions of racemic benzylic bromides with achiral alkylzinc reagents.手性催化的二级烷基亲电试剂与二级烷基金属亲核试剂的交叉偶联反应:外消旋苄基溴与非手性烷基锌试剂的 Negishi 反应。
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Catalytic asymmetric synthesis of secondary nitriles via stereoconvergent Negishi arylations and alkenylations of racemic α-bromonitriles.通过对映选择性 Negishi 芳基化和烯基化外消旋 α-溴代腈,实现了手性仲腈的催化不对称合成。
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New directing groups for metal-catalyzed asymmetric carbon-carbon bond-forming processes: stereoconvergent alkyl-alkyl Suzuki cross-couplings of unactivated electrophiles.新型导向基团在金属催化不对称碳-碳键形成反应中的应用:非活化亲电试剂的立体协同烷基-烷基铃木交叉偶联反应。
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A structure-activity study of Ni-catalyzed alkyl-alkyl Kumada coupling. Improved catalysts for coupling of secondary alkyl halides.镍催化的烷基-烷基库玛达偶联的构效关系研究。改进的用于二级烷基卤化物偶联的催化剂。
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