DFT Study of Unstrained Ketone C-C Bond Activation via Rhodium(I)-Catalyzed Suzuki-Miyaura Cross-Coupling Reactions

Strain Model

Unstrained cyclic ketones can participate in cooperative Suzuki-Miyaura cross-coupling type reaction using rhodium(I)-based catalyst via C-C bond activation. The regioselectivity indicates a trend where the most substituted side is activated and it is controlled by the beta-substituents. In this work, Density Functional Theory (DFT) calculations have been carried out to disclose the underlying mechanism in the reaction of a ketone series and arylboronate using ylidene as ancillary ligand and pyridine as co-catalysts. The computed energies suggest the reductive elimination step with the highest energy while the reductive elimination has the highest energy barrier. By the means of the Activation Strain Model (ASM) of chemical reactivity, it is found that the ketone strain energy released on the oxidative addition does not control the relativity of the OA reactivity, but indeed is the interaction energy between Rh(I) and C-C bond the ruling effect. The effect of the beta-substituents on regioselectivity has been additionally studied.

Carbon-Heteroatom Cross-Coupling via an Electronically Excited Nickel (II) Complex

10.26434/chemrxiv.9736049.v1 ◽

2019 ◽

Author(s):

Randolph Escobar ◽

Jeffrey Johannes

Keyword(s):

Energy Transfer ◽

Functional Groups ◽

Cross Coupling ◽

Reductive Elimination ◽

Aryl Halides ◽

Coupling Reactions ◽

General Methodology ◽

Electronically Excited ◽

Energy Transfer Pathway

<div>While carbon-heteroatom cross coupling reactions have been extensively studied, many methods are specific and</div><div>limited to a set of substrates or functional groups. Reported here is a method that allows for C-O, C-N and C-S cross coupling reactions under one general methodology. We propose that an energy transfer pathway, in which an iridium photosensitizer produces an excited nickel (II) complex, is responsible for the key reductive elimination step that couples aryl halides to 1° and 2° alcohols, anilines, thiophenols, carbamates and sulfonamides.</div>

Ni(COD)(DMFU): A Heteroleptic 16-Electron Precatalyst for 1,2-Diarylation of Alkenes

Synlett ◽

10.1055/a-1344-6040 ◽

2021 ◽

Author(s):

Nana Kim ◽

Van T. Tran ◽

Omar Apolinar ◽

Steven Wisniewski ◽

Martin Eastgate ◽

...

Keyword(s):

Nickel Complex ◽

Active Catalyst ◽

Cross Coupling ◽

Reductive Elimination ◽

Coupling Reactions ◽

Beneficial Effects ◽

Growing Body ◽

Hydride Elimination

Electron-deficient olefin (EDO) ligands are known to promote a variety of nickel-catalyzed cross-coupling reactions, presumably by accelerating the reductive elimination step and preventing undesired β-hydride elimination. While there is a growing body of experimental and computational evidence elucidating the beneficial effects of EDO ligands, significant gaps remain in our understanding of the underlying coordination chemistry of the Ni–EDO species involved. In particular, most procedures rely on in situ assembly of the active catalyst, and there is a paucity of pre-ligated Ni-EDO precatalysts. Herein, we investigate the 16-electron, heteroleptic nickel complex, Ni(COD)(DMFU), and examine the performance of this complex as a precatalyst in 1,2-diarylation of alkenes.

sp2 C–H bond activation in water and catalytic cross-coupling reactions

Chemical Society Reviews ◽

10.1039/c3cs60020c ◽

2013 ◽

Vol 42 (13) ◽

pp. 5744 ◽

Cited By ~ 422

Author(s):

Bin Li ◽

Pierre H. Dixneuf

Keyword(s):

Bond Activation ◽

Cross Coupling ◽

Coupling Reactions ◽

Synthesis of new Pro-PYE ligands as co-catalysts toward Pd-catalyzed Heck–Mizoroki cross coupling reactions

RSC Advances ◽

10.1039/c9ra07912b ◽

2019 ◽

Vol 9 (65) ◽

pp. 37986-38000 ◽

Cited By ~ 2

Author(s):

Naima Munir ◽

Sara Masood ◽

Faroha Liaqat ◽

Muhammad Nawaz Tahir ◽

Sammer Yousuf ◽

...

Keyword(s):

Research Work ◽

Cross Coupling ◽

Coupling Reactions ◽

Co Catalysts ◽

The present research work describes the synthesis of five new ligands containing pyridinium amine, [H2L1][OTf]2–[H2L5][I]2 from two new precursors, [P3Et][I] and [P2Me][CF3SO3].

Density Functional Theory Studies of Negishi Alkyl–Alkyl Cross-Coupling Reactions Catalyzed by a Methylterpyridyl-Ni(I) Complex

The Journal of Organic Chemistry ◽

10.1021/jo702497p ◽

2008 ◽

Vol 73 (10) ◽

pp. 3680-3688 ◽

Cited By ~ 140

Author(s):

Xufeng Lin ◽

David Lee Phillips

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Cross Coupling ◽

Coupling Reactions ◽

Functional Theory ◽

ChemInform Abstract: Pd-Catalyzed sp2-sp Cross-Coupling Reactions Involving C-F Bond Activation in Highly Fluorinated Nitrobenzene Systems.

ChemInform ◽

10.1002/chin.201323050 ◽

2013 ◽

Vol 44 (23) ◽

pp. no-no

Author(s):

Matthew R. Cargill ◽

Graham Sandford ◽

Pinar Kilickiran ◽

Gabriele Nelles

Keyword(s):

Bond Activation ◽

Cross Coupling ◽

Coupling Reactions ◽

Computational Insights into Intramolecular Cross-Coupling of Quaternary Borate Salts

10.26434/chemrxiv.14038736 ◽

2021 ◽

Author(s):

Florian Matz ◽

Arif Music ◽

Dorian Didier ◽

Thomas C. Jagau

Keyword(s):

Organic Synthesis ◽

Energy Barrier ◽

Density Functional ◽

Bond Formation ◽

Cross Coupling ◽

Coupled Cluster ◽

Coupling Reactions ◽

Product Distributions ◽

Borate Salts

Cross-coupling reactions for C-C bond formation represent a cornerstone of organic synthesis. In most cases, they make use of transition metals, which has several downsides. Recently, metal-free alternatives relying on electrochemistry have gained interest. One example of such a reaction is the oxidation of tetraorganoborate salts that initiates aryl-aryl and aryl-alkenyl couplings with promising selectivities. This work investigates the mechanism of this reaction computationally using density functional and coupled-cluster theory. Our calculations reveal a distinct difference between aryl-alkenyl and aryl-aryl couplings: While C-C bond formation occurs irreversibly and without an energy barrier if an alkenyl residue is involved, many intermediates can be identified in aryl-aryl couplings. In the latter case, intramolecular transitions between reaction paths leading to different products are possible. Based on the energy differences between these intermediates, we develop a kinetic model to estimate product distributions for aryl-aryl couplings.<br>

Computational Insights into Intramolecular Cross-Coupling of Quaternary Borate Salts

10.26434/chemrxiv.14038736.v2 ◽

2021 ◽

Author(s):

Florian Matz ◽

Arif Music ◽

Dorian Didier ◽

Thomas C. Jagau

Keyword(s):

Organic Synthesis ◽

Energy Barrier ◽

Density Functional ◽

Bond Formation ◽

Cross Coupling ◽

Coupled Cluster ◽

Coupling Reactions ◽

Product Distributions ◽

Borate Salts

Cross-coupling reactions for C-C bond formation represent a cornerstone of organic synthesis. In most cases, they make use of transition metals, which has several downsides. Recently, metal-free alternatives relying on electrochemistry have gained interest. One example of such a reaction is the oxidation of tetraorganoborate salts that initiates aryl-aryl and aryl-alkenyl couplings with promising selectivities. This work investigates the mechanism of this reaction computationally using density functional and coupled-cluster theory. Our calculations reveal a distinct difference between aryl-alkenyl and aryl-aryl couplings: While C-C bond formation occurs irreversibly and without an energy barrier if an alkenyl residue is involved, many intermediates can be identified in aryl-aryl couplings. In the latter case, intramolecular transitions between reaction paths leading to different products are possible. Based on the energy differences between these intermediates, we develop a kinetic model to estimate product distributions for aryl-aryl couplings.<br>

Deoxygenative Transition-Metal-Promoted Reductive Coupling and Cross-Coupling of Alcohols and Epoxides

Synthesis ◽

10.1055/s-0040-1707269 ◽

2020 ◽

Vol 53 (02) ◽

pp. 267-278

Author(s):

Kenneth M. Nicholas ◽

Chandrasekhar Bandari

Keyword(s):

Transition Metal ◽

Bond Activation ◽

Bond Formation ◽

Cross Coupling ◽

Transition Metal Catalysts ◽

Coupling Reactions ◽

Reductive Coupling ◽

Practical Applications ◽

Carbon Carbon Bond

AbstractThe prospective utilization of abundant, CO2-neutral, renewable feedstocks is driving the discovery and development of new reactions that refunctionalize oxygen-rich substrates such as alcohols and polyols through C–O bond activation. In this review, we highlight the development of transition-metal-promoted reactions of renewable alcohols and epoxides that result in carbon–carbon bond-formation. These include reductive self-coupling reactions and cross-coupling reactions of alcohols with alkenes and arene derivatives. Early approaches to reductive couplings employed stoichiometric amounts of low-valent transition-metal reagents to form the corresponding hydrocarbon dimers. More recently, the use of redox-active transition-metal catalysts together with a reductant has enhanced the practical applications and scope of the reductive coupling of alcohols. Inclusion of other reaction partners with alcohols such as unsaturated hydrocarbons and main-group organometallics has further expanded the diversity of carbon skeletons accessible and the potential for applications in chemical synthesis. Catalytic reductive coupling and cross-coupling reactions of epoxides are also highlighted. Mechanistic insights into the means of C–O activation and C–C bond formation, where available, are also highlighted.1 Introduction2 Stoichiometric Reductive Coupling of Alcohols3 Catalytic Reductive Coupling of Alcohols3.1 Heterogeneous Catalysis3.2 Homogeneous Catalysis4 Reductive Cross-Coupling of Alcohols4.1 Reductive Alkylation4.2 Reductive Addition to Olefins5 Epoxide Reductive Coupling Reactions6 Conclusions and Future Directions