Direct, Iridium-Catalyzed Enantioselective and Regioselective Allylic Etherification with Aliphatic Alcohols

2008 ◽  
Vol 120 (10) ◽  
pp. 1954-1957 ◽  
Author(s):  
Satoshi Ueno ◽  
John F. Hartwig
Keyword(s):  
Aliphatic Alcohols ◽  
Allylic Etherification

scholarly journals Spiro Indane-Based Phosphine-Oxazolines as Highly Efficient P,N Ligands for Enantioselective Pd-Catalyzed Allylic Alkylation of Indoles and Allylic Etherification

Molecules ◽  
2019 ◽  
Vol 24 (8) ◽  
pp. 1575 ◽  
Author(s):  
Zhongxuan Qiu ◽  
Rui Sun ◽  
Kun Yang ◽  
Dawei Teng
Keyword(s):  
Aliphatic Alcohols ◽  
Allylic Alkylation ◽  
Indole Derivatives ◽  
Broad Scope ◽  
Palladium Catalyzed ◽  
Allylic Etherification ◽  
High Yields ◽  
Stereogenic Center ◽  
Optimized Conditions ◽  
Oxazoline Ligands

A series of indane-based phosphine-oxazoline ligands with a spirocarbon stereogenic center were examined for palladium-catalyzed asymmetric allylic alkylation of indoles. Under optimized conditions, high yields (up to 98%) and enantioselectivities (up to 98% ee) were obtained with a broad scope of indole derivatives. The ligand was determined to be the most efficient P,N-ligand for this reaction. Moreover, the ligand was also efficient for Pd-catalyzed asymmetric allylic etherification with hard aliphatic alcohols as nucleophiles.

Simple theoretical models of elimination reactions on polar catalysts; Dehydration reactivity of secondary alcohols on acidic and basic catalysts

1985 ◽  
Vol 50 (4) ◽  
pp. 920-929 ◽  
Author(s):  
Jiří Sedláček
Keyword(s):  
Experimental Data ◽  
Quantum Chemical ◽  
Theoretical Models ◽  
Aliphatic Alcohols ◽  
Secondary Alcohols ◽  
Carbonium Ion ◽  
Dehydration Reactions ◽  
Aromatic Alcohols ◽  
Basic Catalysts ◽  
Simple Models

CNDO/2 calculations for simple models of adsorption and dehydration reactions of secondary aliphatic and aromatic alcohols on polar catalysts are presented. The models involve selected stages of elimination mechanisms of various types (E1, E2 and E1cB elimination). Calculated quantum chemical quantities were correlated with reported experimental data. It is shown that reactivities for the series of substituted phenylethanols correlate very well with the ease of carbonium ion formation. In the case of aliphatic alcohols, calculated quantities correlate generally with the reactivities on SiO2 and are in anticorrelation with the reactivities on Al2O3.NaOH.

Photooxidation effect of cupric complexes on aliphatic alcohols in nonaqueous solutions

1982 ◽  
Vol 47 (8) ◽  
pp. 2061-2068 ◽  
Author(s):  
Jan Sýkora ◽  
Mária Jakubcová ◽  
Zuzana Cvengrošová
Keyword(s):  
Coordination Sphere ◽  
Alcohol Oxidation ◽  
Aliphatic Alcohols ◽  
Oxidation Products ◽  
Molar Ratio ◽  
Quantum Yields ◽  
Nonaqueous Solutions ◽  
The Absolute ◽  
Absolute Quantum

In the photolysis of copper(II)-chloride-alcohol-acetonitrile systems (cCu = 1 mmol l-1, copper(II)-to-chloride molar ratio 1 : 2 to 1 : 8, 10% (v/v) alcohol), Cu(II) is reduced to Cu(I), and methanol, ethanol, 1-propanol, or 1-butanol is oxidized to the corresponding aldehyde, 2-propanol to acetone. In the case of 1-propanol and 1-butanol, chlorinated aldehydes are formed in addition too. The measured quantum yields of the photoreduction of Cu(II) to Cu(I) lay in the range of ΦCu(I) = 4.5 to 40 mmol einstein-1, the absolute quantum yields of the alcohol oxidation products were 2.3 to 47 mmol einstein-1. The photoactive components are chlorocupric complexes [CuClx](2-x)+ (x = 1-4). The presence of complexes with a higher number of chloroligands in the coordination sphere (x = 3, 4) brings about a decrease in the Cu(II) photoreduction rate. The decrease in the photoreduction rate observed in the presence of dioxygen is explained in terms of re-oxidation of copper(I) by the latter, resulting in an increase in the concentration of the photochemically active cupric complexes. The catalytic aspects of the systems in question are discussed with respect to this effect.

Sign in / Sign up

Export Citation Format

Share Document