Mechanistic Studies on the Catalytic Cycle of Metal Fluoride-Catalyzed Allylation Using Allyltrimethoxysilane in Protic Solvents

2003 ◽  
Vol 68 (19) ◽  
pp. 7329-7333 ◽  
Author(s):  
Naohiro Aoyama ◽  
Tomoaki Hamada ◽  
Kei Manabe ◽  
Shū Kobayashi
Keyword(s):  
Catalytic Cycle ◽  
Metal Fluoride ◽  
Mechanistic Studies ◽  
Protic Solvents

Synthesis of diaryldifluoromethanes by Pd-catalyzed difluoroalkylation of arylboronic acids

2015 ◽  
Vol 2 (1) ◽  
pp. 38-41 ◽  
Author(s):  
Ji-Wei Gu ◽  
Wen-Hao Guo ◽  
Xingang Zhang
Keyword(s):  
Electron Transfer ◽  
Catalytic Cycle ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Mechanistic Studies ◽  
Arylboronic Acids

The first example of Pd-catalyzed aryldifluoromethylation of arylboronic acids with readily available aryldifluoromethyl bromides has been described. Preliminary mechanistic studies revealed that a Pd(0)Ln-initiated single electron transfer (SET) pathway is involved in the catalytic cycle.

H2 evolution by a cobalt selenolate electrocatalyst and related mechanistic studies

2017 ◽  
Vol 53 (53) ◽  
pp. 7306-7309 ◽  
Author(s):  
Courtney A. Downes ◽  
Joseph W. Yoo ◽  
Nicholas M. Orchanian ◽  
Ralf Haiges ◽  
Smaranda C. Marinescu
Keyword(s):  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
H2 Evolution

[Co(bds)2][nBu4N] (where bds = 1,2-benzenediselenolate) was identified as an electrocatalyst for H2 evolution. Mechanistic studies indicate that with acid a protonated oligomeric {[Co(bds)2(H)x]x−1}m is formed, which was found to reenter the catalytic cycle and generate H2.

scholarly journals The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)–O Arylation

2020 ◽  
Author(s):  
Reginald Mills ◽  
John. J. Monteith ◽  
Sophie Rousseaux
Keyword(s):  
Cyclopropane Ring ◽  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Design And Optimization ◽  
Redox Active ◽  
Leaving Group

<div><p>The ability to understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp<sup>3</sup>)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp<sup>3</sup>)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active, and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.</p></div>

scholarly journals The Cyclopropane Ring as a Reporter of Radical Leaving-Group Reactivity for Ni-Catalyzed C(sp3)–O Arylation

2020 ◽  
Author(s):  
Reginald Mills ◽  
John. J. Monteith ◽  
Sophie Rousseaux
Keyword(s):  
Cyclopropane Ring ◽  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Reaction Conditions ◽  
Design And Optimization ◽  
Redox Active ◽  
Leaving Group

<div><p>The ability to understand and predict reactivity is highly important for the development of new reactions. In the context of Ni-catalyzed C(sp<sup>3</sup>)–O functionalization, we have developed a unique strategy employing activated cyclopropanols to aid the design and optimization of a redox-active leaving group for C(sp<sup>3</sup>)–O arylation. In this chemistry, the cyclopropane ring acts as a reporter of leaving-group reactivity, since the ring-opened product is obtained under polar (2e) conditions, and the ring-closed product is obtained under radical (1e) conditions. Mechanistic studies demonstrate that the optimal leaving group is redox-active, and are consistent with a Ni(I)/Ni(III) catalytic cycle. The optimized reaction conditions are also used to synthesize a number of arylcyclopropanes, which are valuable pharmaceutical motifs.</p></div>

Boron-Catalyzed Hydrogenative Reduction of Substituted Quinolines to Tetrahydroquinolines with Hydrosilanes

Synlett ◽  
2017 ◽  
Vol 28 (18) ◽  
pp. 2396-2400 ◽  
Author(s):  
Sehoon Park ◽  
Sukbok Chang ◽  
Narasimhulu Gandhamsetty
Keyword(s):  
Initial Step ◽  
Reducing Agents ◽  
Catalytic Cycle ◽  
Transfer Hydrogenation ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Substituted Quinolines ◽  
Optimized Conditions ◽  
Hydroxy Groups

A metal-free procedure for the hydrogenative reduction of substituted N-heteroaromatics has been developed by using hydrosilanes as reducing agents. The optimized conditions were successfully applied to the reactions of quinolines, quinoxalines, and quinoline N-oxides. They were also effective for the reduction of quinolines bearing amino or hydroxy groups, where H2 was evolved through dehydrogenative silylation of the amine or hydroxy moieties. Preliminary mechanistic studies revealed that the initial step in the catalytic cycle involves 1,4-addition of the hydrosilane to the quinoline to give a 1,4-dihydroquinoline; this is followed by (transfer) hydrogenation to deliver the tetrahydroquinoline as the final product.

Kinetic and Mechanistic Studies of the Thermal Isomerization of Bismuth Dithizonate

2000 ◽  
Vol 2000 (4) ◽  
pp. 193-195 ◽  
Author(s):  
Yoshimi Sueishi ◽  
Yoko Takashima
Keyword(s):  
Reaction Mechanisms ◽  
High Pressures ◽  
Thermal Isomerization ◽  
Mechanistic Studies ◽  
Protic Solvents

The isomerization rates of bismuth dithizonate (Bi(HD Z)3) having three dithizone ligands have been measured in various kinds of solvents and at high pressures, and the reaction mechanisms in aprotic and protic solvents are discussed.

Mechanistic Studies of Cp*Ir(III)/Cp*Rh(III)-Catalyzed Branch-Selective Allylic C–H Amidation: Why is Cp*Ir(III) Superior to Cp*Rh(III)?

2021 ◽  
Author(s):  
Nan Ma ◽  
Zheyuan Liu ◽  
Jianhui Huang ◽  
Yanfeng Dang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Catalytic Cycle ◽  
Mechanistic Studies ◽  
Functional Theory

Density functional theory calculations have revealed the mechanism and origins of reactivity and regioselectivity of the Cp*Ir(III)/Cp*Rh(III)-catalyzed allylic C–H amidation of alkenes and dioxazolones. Generally, the catalytic cycle consists of...

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