ChemInform Abstract: Reactivity and Selectivity of ortho-Metalated Rhodium(II) Complexes in C-H Insertion Reactions of α-Diazo Compounds.

ChemInform ◽  
2010 ◽  
Vol 29 (49) ◽  
pp. no-no
Author(s):  
F. ESTEVAN ◽  
P. LAHUERTA ◽  
J. PEREZ-PRIETO ◽  
I. PEREIRA ◽  
S.-E. STIRIBA
Keyword(s):  
Diazo Compounds ◽  
Insertion Reactions

(E)-3-Arylidene-4-diazopyrrolidine-2,5-diones: Preparation and Use in RhII-Catalyzed X–H Insertion Reactions towards Novel, Medicinally Important Michael Acceptors

Synthesis ◽  
2020 ◽  
Author(s):  
Dmitry Dar’in ◽  
Mikhail Krasavin ◽  
Evgeny Chupakhin ◽  
Martha Gecht ◽  
Alexander Ivanov ◽  
...  
Keyword(s):  
Thioredoxin Reductase ◽  
Diazo Compounds ◽  
Transfer Reactions ◽  
Geometrical Configuration ◽  
Insertion Reactions ◽  
Michael Acceptors ◽  
Substituted 1

AbstractThe use of readily available 1-aryl-3-arylidenepyrrolidine-2,5-diones in high yielding direct diazo-transfer reactions and subsequent involvement of the resulting diazo compounds in RhII-catalyzed O–H, S–H, and N–H insertion reactions delivered 4-substituted 1-aryl-3-arylidenepyrrolidine-2,5-diones of defined regiochemistry and geometrical configuration. These products are intended to be studied as Michael acceptors capable of inhibiting thioredoxin reductase, a promising cancer target.

Halodiazoacetates as useful tools for selective halo-functionalization

2011 ◽  
Vol 83 (3) ◽  
pp. 565-575 ◽  
Author(s):  
Hanne Therese Bonge ◽  
Tore Hansen
Keyword(s):  
Density Functional Theory ◽  
Dft Calculations ◽  
Density Functional ◽  
Diazo Compounds ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Kinetic Activity ◽  
Synthetic Utility ◽  
Insight Into ◽  
Halocarbonyl Compounds

The halodiazoacetates are a group of synthetically useful halogenated diazo compounds that can be used in Rh(II)-catalyzed carbenoid reactions. In the reactions between the halodiazoacetates and electron-rich, sterically unhindered alkenes, halocyclopropanes are formed in good to excellent yields. The halodiazoacetates also react well in C–H and Si–H insertion reactions, broadening the synthetic utility of these reactions. The products of the reactions are synthetically useful α-halocarbonyl compounds. Density functional theory (DFT) calculations have given insight into the mechanism of the cyclopropanation and C–H insertion reactions of the halodiazoacetates, and have also shown that the halodiazoacetates have a particularly high kinetic activity.

Silica-supported HClO4 promotes catalytic solvent- and metal-free O–H insertion reactions with diazo compounds

2018 ◽  
Vol 20 (19) ◽  
pp. 4547-4556 ◽  
Author(s):  
Rafael Douglas C. Gallo ◽  
Antonio C. B. Burtoloso
Keyword(s):  
Diazo Compounds ◽  
Bronsted Acid ◽  
Brønsted Acid ◽  
Insertion Reactions ◽  
Metal Free ◽  
Brönsted Acid

An eco-friendly and metal-free protocol to perform O–H insertion reactions, using only 0.3 mol% of a recyclable silica-immobilized BrØnsted acid is described.

scholarly journals Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study

2021 ◽  
Author(s):  
Croix Laconsay ◽  
Anna Pla-Quintana ◽  
Dean Tantillo
Keyword(s):  
Density Functional ◽  
Computational Study ◽  
Density Functional Theory Calculations ◽  
Diazo Compounds ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Axial Ligation ◽  
Donor Acceptor ◽  
Solvent Molecules ◽  
Dirhodium Complexes

Density functional theory calculations were used to systematically explore the effects of axial ligation by solvent molecules on the reactivity and selectivity of dirhodium tetracarboxylates with diazo compounds in the context of C–H insertion into propane. Insertions on three types of diazo compounds—acceptor/acceptor, donor/acceptor, and donor/donor—promoted by dirhodium tetraformate were tested with and without axial solvent ligation for no surrounding solvent, dichloromethane, isopropanol, and acetonitrile. Magnitudes, origins, and consequences of structural and electronic changes arising from axial ligation were characterized. The results suggest that axial ligation affects barriers for N2 extrusion and C–H insertion, the former to a larger extent.

Rhodium-Catalyzed B–H Bond Insertion Reactions of Unstabilized Diazo Compounds Generated in Situ from Tosylhydrazones

2018 ◽  
Vol 140 (34) ◽  
pp. 10663-10668 ◽  
Author(s):  
Yue Pang ◽  
Qiao He ◽  
Zi-Qi Li ◽  
Ji-Min Yang ◽  
Jin-Han Yu ◽  
...  
Keyword(s):  
Diazo Compounds ◽  
Insertion Reactions

scholarly journals The Power of Iron Catalysis in Diazo Chemistry

Synthesis ◽  
2020 ◽  
Vol 53 (01) ◽  
pp. 79-94
Author(s):  
Thierry Ollevier ◽  
Virginie Carreras ◽  
Nour Tanbouza
Keyword(s):  
Short Review ◽  
Metal Catalysts ◽  
Diazo Compounds ◽  
Cycloaddition Reactions ◽  
Insertion Reactions ◽  
Iron Catalysis ◽  
Recent Advances ◽  
Olefination Reactions

AbstractThe use of iron catalysis to enable reactions with diazo compounds has emerged as a valuable tool to forge carbon–carbon or carbon–heteroatom bonds. While diazo compounds are often encountered with toxic and expensive metal catalysts, such as Rh, Ru, Pd, Ir, and Cu, a resurgence of Fe catalysis has been observed. This short review will showcase and highlight the recent advances in iron-mediated reactions of diazo compounds.1 Introduction2 Insertion Reactions2.1 Insertion into B–H Bonds2.2 Insertion into Si–H Bonds2.3 Insertion into N–H Bonds2.4 Insertion into S–H bonds3 Ylide Formation and Subsequent Reactions3.1 Doyle–Kirmse Rearrangement3.2 [1,2]-Stevens and Sommelet–Hauser Rearrangements3.3 Olefination Reactions3.4 Cycloaddition Reactions3.5 gem-Difluoroalkenylation4 Three-Component Reactions5 Miscellaneous6 Conclusion

scholarly journals Effects of Axial Solvent Coordination to Dirhodium Complexes on Reactivity and Selectivity in C–H Insertion Reactions: A Computational Study

2021 ◽  
Author(s):  
Croix Laconsay ◽  
Anna Pla-Quintana ◽  
Dean Tantillo
Keyword(s):  
Density Functional ◽  
Computational Study ◽  
Density Functional Theory Calculations ◽  
Diazo Compounds ◽  
Insertion Reactions ◽  
Functional Theory ◽  
Axial Ligation ◽  
Donor Acceptor ◽  
Solvent Molecules ◽  
Dirhodium Complexes

Density functional theory calculations were used to systematically explore the effects of axial ligation by solvent molecules on the reactivity and selectivity of dirhodium tetracarboxylates with diazo compounds in the context of C–H insertion into propane. Insertions on three types of diazo compounds—acceptor/acceptor, donor/acceptor, and donor/donor—promoted by dirhodium tetraformate were tested with and without axial solvent ligation for no surrounding solvent, dichloromethane, isopropanol, and acetonitrile. Magnitudes, origins, and consequences of structural and electronic changes arising from axial ligation were characterized. The results suggest that axial ligation affects barriers for N2 extrusion and C–H insertion, the former to a larger extent.

Effect of Tethered, Axial Thioether Coordination on Rhodium(II)-Catalyzed Silyl-Hydrogen Insertion

2019 ◽  
Author(s):  
William Sheffield ◽  
Anthony Abshire ◽  
Ampofo Darko
Keyword(s):  
Computational Modeling ◽  
Diazo Compounds ◽  
Insertion Reactions ◽  
Hydrogen Insertion

The effect of tethering a thioether to a rhodium paddlewheel complex are evaluated in diazo-mediated Si–H insertion reactions. This study provides further evidence for the benefits of incorporating thioethers into the rhodium paddlewheel motif. When compared to a non-tethered complex, the <i>in situ </i>carbenoid formation and subsequent Si–H insertion are not impeded by the thioether tether, improves yields by up to 12%, and is more selective for diazo compounds when compared to non-tethered catalysts. Computational modeling of the complexes at the M06-2X/def2-TZVPP level of theory is also presented in order to rationalize the results.

Sign in / Sign up

Export Citation Format

Share Document