scholarly journals Unraveling innate substrate control in site-selective palladium-catalyzed C–H heterocycle functionalization

2016 ◽  
Vol 7 (6) ◽  
pp. 3900-3909 ◽  
Author(s):  
Hwanho Choi ◽  
Minsik Min ◽  
Qian Peng ◽  
Dahye Kang ◽  
Robert S. Paton ◽  
...  
Keyword(s):  
Experimental Studies ◽  
Direct Arylation ◽  
Palladium Catalyzed ◽  
Site Selective ◽  
Coupling Partner

Pd(ii)-catalyzed direct arylation of chromones and enaminones gives divergent site-selectivities. Computational and experimental studies reveal a switch in mechanism, from a C3-selective CMD mechanism to a C2-selective carbopalladation pathway. This model accounts for the opposite selectivities of enaminone and chromone, and also correctly predicts selectivities for the C–H functionalization of heteroaromatic substrates as a function of the coupling partner.

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

Palladium-catalyzed site-selective arylation of aliphatic ketones enabled by a transient ligand

2018 ◽  
Vol 54 (22) ◽  
pp. 2759-2762 ◽  
Author(s):  
Lei Pan ◽  
Ke Yang ◽  
Guigen Li ◽  
Haibo Ge
Keyword(s):  
Functional Group ◽  
Direct Arylation ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Palladium Catalyzed ◽  
High Site ◽  
Site Selective

A direct arylation of C–H bonds of ketones enabled by a cheap and commercially available transient ligand with high site-selectivity and functional group compatibility is reported.

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

scholarly journals Copper-catalyzed Site-selective Direct Arylation of Triptycene

2020 ◽  
Vol 49 (6) ◽  
pp. 689-692
Author(s):  
Keisuke Ueno ◽  
Yuji Nishii ◽  
Masahiro Miura
Keyword(s):  
Direct Arylation ◽  
Site Selective

scholarly journals Palladium-catalyzed direct arylation and cyclization of o-iodobiaryls to a library of tetraphenylenes

2016 ◽  
Vol 6 (1) ◽  
Author(s):  
Chendan Zhu ◽  
Yue Zhao ◽  
Di Wang ◽  
Wei-Yin Sun ◽  
Zhuangzhi Shi
Keyword(s):  
Direct Arylation ◽  
Palladium Catalyzed

ChemInform Abstract: Palladium-Catalyzed Direct Arylation of Thiophenes Bearing SO2R Substituents.

ChemInform ◽  
2011 ◽  
Vol 42 (49) ◽  
pp. no-no
Author(s):  
Charles Beromeo Bheeter ◽  
Jitendra K. Bera ◽  
Henri Doucet
Keyword(s):  
Direct Arylation ◽  
Palladium Catalyzed

ChemInform Abstract: Formyl Substituent at C-4 of Pyrazoles: A Temporary Protecting Group for Regioselective Palladium-Catalyzed Direct Arylation at C-5.

ChemInform ◽  
2015 ◽  
Vol 46 (4) ◽  
pp. no-no
Author(s):  
Imen Smari ◽  
Chiraz Youssef ◽  
Kedong Yuan ◽  
Anissa Beladhria ◽  
Hamed Ben Ammar ◽  
...  
Keyword(s):  
Protecting Group ◽  
Direct Arylation ◽  
Palladium Catalyzed

ChemInform Abstract: Palladium-Catalyzed Direct Arylation Reactions

ChemInform ◽  
2010 ◽  
Vol 41 (9) ◽  
Author(s):  
Masahiro Miura ◽  
Tetsuya Satoh
Keyword(s):  
Direct Arylation ◽  
Palladium Catalyzed

Catalyst-Controlled Site-Selective N-H and C3-Arylation of Carba-zole via Carbene Transfer Reactions

2021 ◽  
Author(s):  
Sourav Sekhar Bera ◽  
Srishti Ballabh Bahukhandi ◽  
Claire Empel ◽  
Rene M Koenigs
Keyword(s):  
Transfer Reactions ◽  
Palladium Acetate ◽  
Direct Arylation ◽  
Carbene Transfer ◽  
A Site ◽  
Site Selective

A site-selective direct arylation reaction of carbazole and other N-heterocycles with diazo-naphthalen-2(1H)-ones has been developed. While Au(I)-NHC catalysts lead to selective C3-arylation, palladium acetate allows for selective N-H arylation, displaying...

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