scholarly journals Understanding the Influence of Donor‐Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6F5)3 Towards Carbene Formation

2021 ◽  
Author(s):  
Rasool Babaahmadi ◽  
Ayan Dasgupta ◽  
Christopher J. T. Hyland ◽  
Brian F . Yates ◽  
Rebecca Melen ◽  
...  
Keyword(s):  
Diazo Compounds ◽  
Donor Acceptor ◽  
Catalyst Efficiency

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.

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.

scholarly journals Copper-Catalyzed Insertion of Diazo Compounds into Vinyl Hypervalent Iodine Reagents to Generate Allylic Esters

2019 ◽  
Author(s):  
Guillaume Pisella ◽  
Alec Gagnebin ◽  
Jerome Waser
Keyword(s):  
Functional Groups ◽  
Allylic Alcohol ◽  
Diazo Compounds ◽  
Hypervalent Iodine ◽  
Aryl Iodide ◽  
Broad Scope ◽  
Donor And Acceptor ◽  
Leaving Group ◽  
Donor Acceptor ◽  
Allylic Esters

An unprecedented copper(I)-catalyzed vinylation of (donor)-acceptor diazo compounds with VinylBenziodoXolone reagents (VBX) as partners is reported. The transformation tolerates variation of both donor- and acceptor substituents on the diazo compounds, delivering the corresponding benzoylated allylic alcohol products in good to excellent yields. Through the development of a protocol for the synthesis of functionalized alkanes-, dienes- and enynes-substituted VBX reagents, a broad scope of substituents on the alkene could be accessed. The obtained products contain synthetically versatile functional groups, such as an aryl iodide, an ester and an allylic leaving group, enabling selective further modification.

scholarly journals Copper-Catalyzed Insertion of Diazo Compounds into Vinyl Hypervalent Iodine Reagents to Generate Allylic Esters

2019 ◽  
Author(s):  
Guillaume Pisella ◽  
Alec Gagnebin ◽  
Jerome Waser
Keyword(s):  
Functional Groups ◽  
Allylic Alcohol ◽  
Diazo Compounds ◽  
Hypervalent Iodine ◽  
Aryl Iodide ◽  
Broad Scope ◽  
Donor And Acceptor ◽  
Leaving Group ◽  
Donor Acceptor ◽  
Allylic Esters

An unprecedented copper(I)-catalyzed vinylation of (donor)-acceptor diazo compounds with VinylBenziodoXolone reagents (VBX) as partners is reported. The transformation tolerates variation of both donor- and acceptor substituents on the diazo compounds, delivering the corresponding benzoylated allylic alcohol products in good to excellent yields. Through the development of a protocol for the synthesis of functionalized alkanes-, dienes- and enynes-substituted VBX reagents, a broad scope of substituents on the alkene could be accessed. The obtained products contain synthetically versatile functional groups, such as an aryl iodide, an ester and an allylic leaving group, enabling selective further modification.

Gold-catalyzed para-selective C–H bond alkylation of benzene derivatives with donor/acceptor-substituted diazo compounds

2017 ◽  
Vol 53 (73) ◽  
pp. 10164-10167 ◽  
Author(s):  
Ben Ma ◽  
Jiaojiao Wu ◽  
Lu Liu ◽  
Junliang Zhang
Keyword(s):  
Diazo Compounds ◽  
Benzene Derivatives ◽  
Alkylation Of Benzene ◽  
Donor Acceptor

A gold(i)-catalyzed cascade C–H functionalization of unactivated arenes with α-aryl α-diazoesters with electron-withdrawing groups has been developed.

scholarly journals A One-pot Access to Diastereoselective Benzo[5,6]oxepino[2,3-c]pyrroles via Formal (5+2)-Annulation of Donor-/Acceptor-Type Aryl Vinyl diazosuccinimide with Ketones Under Silver Catalysis

2021 ◽  
Author(s):  
Dr. Ramakrishna G. Bhat ◽  
Debasish Laha ◽  
Kajal B. Meher ◽  
Onkar S. Bankar
Keyword(s):  
Diazo Compounds ◽  
Diastereoselective Synthesis ◽  
Methyl Ketones ◽  
Nmr Studies ◽  
One Pot ◽  
Efficient Catalyst ◽  
Silver Catalysis ◽  
Single Diastereomer ◽  
Donor Acceptor ◽  
Plausible Mechanism

A silver triflimide catalyzed one-pot protocol for the diastereoselective synthesis of dihydrobenzoxepines has been developed. Silver triflimide found to be an efficient catalyst for the formal (5+2)-cycloaddition to access dihydrobenzoxepines as a single diastereomer using vinyl diazo compounds as 5-C-synthons and ketones. An unmet challenge of utilizing the donor-/acceptor-type vinyl diazosuccinimides as 5-C-synthons under silver-catalysis is presented. This protocol found to be highly regio-, chemo- and diastereoselective, and works well with aliphatic as well as aromatic methyl ketones bearing electron deactivating as well as donating groups to afford dihydrobenzo[5,6]oxepino[2,3-c]pyrroles with a broad substrates scope. The control experiments and time dependent NMR studies revealed the plausible mechanism of this transformation. The protocol also proved to be scalable on the gram scale synthesis.

scholarly journals Bis(imino)pyridine iron complexes for catalytic carbene transfer reactions

2019 ◽  
Vol 10 (34) ◽  
pp. 7958-7963 ◽  
Author(s):  
Ban Wang ◽  
Isaac G. Howard ◽  
Jackson W. Pope ◽  
Eric D. Conte ◽  
Yongming Deng
Keyword(s):  
Iron Complexes ◽  
Iron Complex ◽  
Diazo Compounds ◽  
Transfer Reactions ◽  
Donor Acceptor ◽  
Carbene Transfer ◽  
First Time

The bis(imino)pyridine iron complex, for the first time, is developed as an effective metal carbene catalyst for carbene transfer reactions of donor–acceptor diazo compounds.

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