Hydride Transfer Reduction of Carbonyls by a Rhodium(I) Complex: A Theoretical Study. 1. The Two-Step Mechanism

2000 ◽  
Vol 19 (8) ◽  
pp. 1589-1598 ◽  
Author(s):  
Vincent Guiral ◽  
Françoise Delbecq ◽  
Philippe Sautet
Keyword(s):  
Theoretical Study ◽  
Hydride Transfer ◽  
Step Mechanism

scholarly journals Asymmetric Cyanation of Activated Olefins with Ethyl Cyanoformate Catalyzed by Ti(IV)-Catalyst: A Theoretical Study

Catalysts ◽  
2020 ◽  
Vol 10 (9) ◽  
pp. 1079
Author(s):  
Zhishan Su ◽  
Changwei Hu ◽  
Nasir Shahzad ◽  
Chan Kyung Kim
Keyword(s):  
Transition State ◽  
Self Assembly ◽  
Theoretical Study ◽  
Activation Barrier ◽  
Cinchona Alkaloid ◽  
Activation Process ◽  
Construction Step ◽  
Dual Activation ◽  
Membered Transition State ◽  
Step Mechanism

The reaction mechanism and origin of asymmetric induction for conjugate addition of cyanide to the C=C bond of olefin were investigated at the B3LYP-D3(BJ)/6-31+G**//B3LYP-D3(BJ)/6-31G**(SMD, toluene) theoretical level. The release of HCN from the reaction of ethyl cyanoformate (CNCOOEt) and isopropanol (HOiPr) was catalyzed by cinchona alkaloid catalyst. The cyanation reaction of olefin proceeded through a two-step mechanism, in which the C-C bond construction was followed by H-transfer to generate a cyanide adduct. For non-catalytic reaction, the activation barrier for the rate-determining C-H bond construction step was 34.2 kcal mol−1, via a four-membered transition state. The self-assembly Ti(IV)-catalyst from tetraisopropyl titanate, (R)-3,3′-disubstituted biphenol, and cinchonidine accelerated the addition of cyanide to the C=C double bond by a dual activation process, in which titanium cation acted as a Lewis acid to activate the olefin and HNC was orientated by hydrogen bonding. The steric repulsion between the 9-phenanthryl at the 3,3′-position in the biphenol ligand and the Ph group in olefin raised the Pauli energy (ΔE≠Pauli) of reacting fragments at the re-face attack transition state, leading to the predominant R-product.

Theoretical Study of the Mechanism of the Hydride Transfer between Ferredoxin–NADP+ Reductase and NADP+: The Role of Tyr303

2012 ◽  
Vol 134 (50) ◽  
pp. 20544-20553 ◽  
Author(s):  
Isaias Lans ◽  
Milagros Medina ◽  
Edina Rosta ◽  
Gerhard Hummer ◽  
Mireia Garcia-Viloca ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Hydride Transfer

New insights in atmospheric acid-catalyzed gas phase hydrolysis of formaldehyde: a theoretical study

RSC Advances ◽  
2015 ◽  
Vol 5 (42) ◽  
pp. 32941-32949 ◽  
Author(s):  
Fang-Yu Liu ◽  
Xing-Feng Tan ◽  
Zheng-Wen Long ◽  
Bo Long ◽  
Wei-Jun Zhang
Keyword(s):  
Nitric Acid ◽  
Gas Phase ◽  
Theoretical Study ◽  
Acid Catalyzed ◽  
Hydrolysis Of ◽  
Step Mechanism

A two-step mechanism of the gas phase hydrolysis of formaldehyde catalyzed by nitric acid.

scholarly journals A theoretical study of the hydride transfer between 1-Adamantyl cation and isopentane

2010 ◽  
Vol 21 (12) ◽  
pp. 2180-2183 ◽  
Author(s):  
Patrícia D. de Oliveira ◽  
Nilton Rosenbach Jr. ◽  
Alex P. A. dos Santos ◽  
Claudio J. A. Mota
Keyword(s):  
Theoretical Study ◽  
Hydride Transfer
Sign in / Sign up

Export Citation Format

Share Document