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

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.

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.

Synthetic applications of the O-H insertion reactions of carbenes and carbenoids derived from diazocarbonyl and related diazo compounds

Tetrahedron ◽  
1995 ◽  
Vol 51 (40) ◽  
pp. 10811-10843 ◽  
Author(s):  
David J. Miller ◽  
Christopher J. Moody
Keyword(s):  
Diazo Compounds ◽  
Insertion Reactions

In situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement: copper-catalyzed synthesis of unsymmetrical diacylglycine esters

2016 ◽  
Vol 14 (45) ◽  
pp. 10723-10732 ◽  
Author(s):  
Jijun Chen ◽  
Ying Shao ◽  
Liang Ma ◽  
Meihua Ma ◽  
Xiaobing Wan
Keyword(s):  
Carboxylic Acid ◽  
Diazo Compounds ◽  
Acid Nitrile ◽  
In Situ Generation

A novel in situ generation of nitrilium from nitrile ylide and the subsequent Mumm rearrangement of carboxylic acid, nitrile, and diazo compounds gave various unsymmetrical diacylglycine esters.

(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.

ChemInform Abstract: INSERTION REACTIONS OF DIAZO COMPOUNDS WITH SOME SELENIUM(II) ELECTROPHILES

1985 ◽  
Vol 16 (37) ◽  
Author(s):  
T. G. BACK ◽  
R. G. KERR
Keyword(s):  
Diazo Compounds ◽  
Insertion Reactions

Laser in-situ synthesis of SnO2/N-doped graphene nanocomposite with enhanced lithium storage properties based on both alloying and insertion reactions

2017 ◽  
Vol 422 ◽  
pp. 645-653 ◽  
Author(s):  
Xiaoxiao Lu ◽  
Guolong Wu ◽  
Qinqin Xiong ◽  
Haiying Qin ◽  
Zhenguo Ji ◽  
...  
Keyword(s):  
In Situ Synthesis ◽  
Insertion Reactions ◽  
Lithium Storage ◽  
Doped Graphene ◽  
Graphene Nanocomposite ◽  
Storage Properties

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.

scholarly journals Preparation and in situ use of unstable N-alkyl a-diazo-g-butyrolactams in RhII-catalyzed X-H insertion reactions

2020 ◽  
Author(s):  
Maria Eremeyeva ◽  
Daniil Zhukovsky ◽  
Dmitry Dar'in ◽  
Mikhail Krasavin
Keyword(s):  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Insertion Reactions ◽  
Sterically Hindered

N-Alkyl a-diazo-g-butyrolactams previously found to be unstable and undergo unproductive dimerization to bis-hydrazones, were successfully converted immediately to various X-H insertion products with alcohols, aromatic amines and thiols via an in situ RhII-catalyzed reaction. With aliphatic amines or unreactive, sterically hindered anilines, the reaction tends to yield enamine adducts.

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.

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