Redox-neutral ortho -C–H amination of pinacol arylborates via palladium( ii )/norbornene catalysis for aniline synthesis

A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible w...

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Published inChemical science (Cambridge) Vol. 10; no. 36; pp. 8384 - 8389
Main Authors Chen, Shuqing, Wang, Peng, Cheng, Hong-Gang, Yang, Chihui, Zhou, Qianghui
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 28.09.2019
Royal Society of Chemistry
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Abstract A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso -protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
AbstractList A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso-protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral -C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral -protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso -protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines. A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso -protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso-protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally diverse anilines is reported. This method is scalable, robust (tolerance of air and moisture), phosphine ligand-free, and compatible with a wide range of functionalities. These practical features make this reaction amenable for industry. A plethora of synthetically very useful halogenated anilines, which often cannot be prepared via other transition-metal-catalyzed aminations, are readily produced using this method. Particularly, the orthogonal reactivity between pinacol arylborates and aryl iodides is demonstrated. Preliminary deuterium-labeling studies reveal a redox-neutral ipso-protonation mechanism of this process, which will surely inspire the future development of this field. Overall, the exceptionally broad scope (47 examples) and reliability of this procedure, together with the wide availability of pinacol arylborates, make this chemistry a valuable addition to the existing methods for aniline synthesis.
Author Wang, Peng
Cheng, Hong-Gang
Yang, Chihui
Chen, Shuqing
Zhou, Qianghui
AuthorAffiliation b The Institute for Advanced Studies , Wuhan University , 430072 , Wuhan , China . Email: qhzhou@whu.edu.cn
a Sauvage Center for Molecular Sciences , Engineering Research Center of Organosilicon Compounds & Materials (Ministry of Education) , College of Chemistry and Molecular Sciences , Wuhan University , Wuhan , 430072 , China
AuthorAffiliation_xml – name: b The Institute for Advanced Studies , Wuhan University , 430072 , Wuhan , China . Email: qhzhou@whu.edu.cn
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Issue 36
Keywords AROMATIC FUNCTIONALIZATION
PALLADIUM
NORBORNENE
CARBON
ARYLATION
ELECTROPHILIC AMINATION
ARYL IODIDES
CATELLANI REACTION
PD/NORBORNENE
ARYLBORONIC ACIDS
Language English
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Snippet A palladium( ii )/norbornene cooperative catalysis enabled redox-neutral ortho -C–H amination of pinacol aryl- or heteroarylborates for the synthesis of...
A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C-H amination of pinacol aryl- or heteroarylborates for the synthesis of...
A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral -C-H amination of pinacol aryl- or heteroarylborates for the synthesis of structurally...
A palladium(ii)/norbornene cooperative catalysis enabled redox-neutral ortho-C–H amination of pinacol aryl- or heteroarylborates for the synthesis of...
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SubjectTerms Aniline
Aromatic compounds
Catalysis
Chemical synthesis
Chemistry
Chemistry, Multidisciplinary
Deuterium
Iodides
Organic chemistry
Palladium
Physical Sciences
Protonation
Science & Technology
Transition metals
Title Redox-neutral ortho -C–H amination of pinacol arylborates via palladium( ii )/norbornene catalysis for aniline synthesis
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https://www.ncbi.nlm.nih.gov/pubmed/31803416
https://www.proquest.com/docview/2292108561
https://www.proquest.com/docview/2322138593
https://pubmed.ncbi.nlm.nih.gov/PMC6839810
Volume 10
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