Oxidative Addition of Aryl and Benzyl Trifluoroacetates to Zerovalent Palladium Complexes with Two Modes of C–O Bond Cleavage Processes

1999 ◽  
Vol 72 (4) ◽  
pp. 799-803 ◽  
Author(s):  
Kazuhiro Nagayama ◽  
Isao Shimizu ◽  
Akio Yamamoto
Keyword(s):  
Bond Cleavage ◽  
Oxidative Addition ◽  
Palladium Complexes

scholarly journals Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

2017 ◽  
Vol 836-837 ◽  
pp. 17-25 ◽  
Author(s):  
Minna M. Karjalainen ◽  
Torben Wiegand ◽  
J. Mikko Rautiainen ◽  
Andreas Wagner ◽  
Helmar Görls ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Oxidative Addition

scholarly journals Controlling Non-Native B12 Reactivity and Catalysis in the Transcription Factor CarH

2021 ◽  
Author(s):  
Xinhang Yang ◽  
Benjamin H. R. Gerroll ◽  
Yuhua Jiang ◽  
Amardeep Kumar ◽  
Yasmine S. Zubi ◽  
...  
Keyword(s):  
Transcription Factor ◽  
Vitamin B12 ◽  
Transcription Regulation ◽  
Bond Cleavage ◽  
Oxidative Addition ◽  
Mechanistic Studies ◽  
Organic Transformations ◽  
Carbon Bond ◽  
Wide Range ◽  
Hydride Elimination

Vitamin B12 derivatives catalyze a wide range of organic transformations, but B12-dependent enzymes are underutilized in biocatalysis relative to other metalloenzymes. In this study, we engineered a variant of the transcription factor CarH, called CarH*, that catalyzes styrene C-H alkylation with improved yield and selectivity relative to B12 itself. While the native function of CarH involves transcription regulation via AdoCbl Co(III)-carbon bond cleavage and β-hydride elimination to generate 4’,5’-didehydroadenosine, CarH*-catalyzed styrene alkylation proceeds via non-native oxidative addition and olefin addition coupled with a native-like β-hydride elimination. Mechanistic studies on this reaction echo findings from earlier studies on AdoCbl homolysis under strong cage conditions to suggest that CarH* can enable non-native radical chemistry with improved selectivity relative to B12 itself. These findings lay the groundwork for the development of B12-dependent enzymes as catalysts for a wide range of non-native transformations.

scholarly journals Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands

2020 ◽  
Vol 49 (2) ◽  
pp. 322-335 ◽  
Author(s):  
Tomás G. Santiago ◽  
Carmen Urbaneja ◽  
Eleuterio Álvarez ◽  
Elena Ávila ◽  
Pilar Palma ◽  
...  
Keyword(s):  
Ligand Exchange ◽  
Oxidative Addition ◽  
Palladium Complexes ◽  
Addition Reactions ◽  
Acid Base

Ligand exchange and oxidative addition reactions allow the synthesis of Ni(ii) and Pd(ii) complexes with deprotonable iminophosphine ligands. The acid–base behavior of iminophosphine ligands coordinated to organometallic Ni(ii) fragments is analyzed.

Oxidative Addition Promoted C–C Bond Cleavage in Rh-Mediated Cyclopropenone Activation: A DFT Study

ACS Catalysis ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 10876-10886 ◽  
Author(s):  
Yixin Luo ◽  
Chunhui Shan ◽  
Song Liu ◽  
Tao Zhang ◽  
Lei Zhu ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Oxidative Addition ◽  
Dft Study

Transition-Metal-Catalyzed Synthesis of Organophosphorus Compounds Involving P–P Bond Cleavage

Synthesis ◽  
2020 ◽  
Vol 52 (19) ◽  
pp. 2795-2806 ◽  
Author(s):  
Mieko Arisawa
Keyword(s):  
Transition Metal ◽  
Organophosphorus Compounds ◽  
Bond Cleavage ◽  
Palladium Complexes ◽  
Addition Reactions ◽  
Phosphonium Salts ◽  
Substitution Reactions ◽  
Sulfonic Acids ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Organophosphorus compounds are used as drugs, pesticides, detergents, food additives, flame retardants, synthetic reagents, and catalysts, and their efficient synthesis is an important task in organic synthesis. To synthesize novel functional organophosphorus compounds, transition-metal-catalyzed methods have been developed, which were previously considered difficult because of the strong bonding that occurs between transition metals and phosphorus. Addition reactions of triphenylphosphine and sulfonic acids to unsaturated compounds in the presence of a rhodium or palladium catalyst lead to phosphonium salts, in direct contrast to the conventional synthesis involving substitution reactions of organohalogen compounds. Rhodium and palladium complexes catalyze the cleavage of P–P bonds in diphosphines and polyphosphines and can transfer organophosphorus groups to various organic compounds. Subsequent substitution and addition reactions proceed effectively, without using a base, to provide various novel organophosphorus compounds.1 Introduction2 Transition-Metal-Catalyzed Synthesis of Phosphonium Salts by Addition Reactions of Triphenylphosphine and Sulfonic Acids3 Rhodium-Catalyzed P–P Bond Cleavage and Exchange Reactions4 Transition-Metal-Catalyzed Substitution Reactions Using Diphosphines4.1 Reactions Involving Substitution of a Phosphorus Group by P–P Bond Cleavage4.2 Related Substitution Reactions of Organophosphorus Compounds4.3 Substitution Reactions of Acid Fluorides Involving P–P Bond Cleavage of Diphosphines5 Rhodium-Catalyzed P–P Bond Cleavage and Addition Reactions6 Rhodium-Catalyzed P–P Bond Cleavage and Insertion Reactions Using Polyphosphines7 Conclusions

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