Prediction of the Absolute Configurations of the Enantiomers of Racemic Primary and Secondary Alcohols and Primary Amines by Kinetic Resolution with (2R,3R)-2,3-Diacetoxysuccinic Anhydride

1979 ◽  
Vol 32 (12) ◽  
pp. 2625 ◽  
Author(s):  
KH Bell
Keyword(s):  
Free Energy ◽  
Prediction Model ◽  
Kinetic Resolution ◽  
Primary Amines ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
The Absolute ◽  
Conformational Free Energy

The absolute configurations of the enantiomers of a variety of racemic secondary and primary alcohols and racemic primary amines have been correctly predicted from the results of kinetic resolution with (2R,3R)-2,3-diacetoxysuccinic anhydride. In the prediction model (1), allocation of relative sizes to the groups attached to the chiral centre was based on conformational free energy differences.

Studies on transition-metal nitrido and oxo complexes. Part 20. Oxoruthenates and oxo-osmates in oxidation catalysis; cis-[Os(OH)2O4]2- as a catalytic oxidant for primary amines and for alcohols

2001 ◽  
Vol 79 (5-6) ◽  
pp. 598-606 ◽  
Author(s):  
William P Griffith ◽  
Maria Suriaatmaja
Keyword(s):  
Raman Spectroscopy ◽  
Transition Metal ◽  
Carboxylic Acids ◽  
Oxidative Dehydrogenation ◽  
Alcohol Oxidation ◽  
Oxidation Catalysis ◽  
Primary Amines ◽  
Secondary Alcohols ◽  
Primary Alcohols ◽  
Aromatic And Aliphatic Amines

cis-[Os(OH)2O4]2– with [Fe(CN)6]3– and other co-oxidants has been studied as a catalytic reagent for the oxidative dehydrogenation of primary aromatic and aliphatic amines to nitriles, the oxidation of primary alcohols to carboxylic acids and of secondary alcohols to ketones. Electronic and Raman spectroscopy have been used to elucidate the nature of the oxoruthenates and oxo-osmates present in a number of reported organic oxidations catalyzed by ruthenium and osmium species.Key words: oxidation catalysis, ruthenium, osmium, amine dehydrogenation, alcohol oxidation.

Regioselectivity and stereoselectivity in the reaction of cis-1,2,2-Trimethylcyclopentane-1,3-dicarboxylic anhydride (cis-camphoric anhydride) with chiral primary amines

1981 ◽  
Vol 34 (3) ◽  
pp. 665 ◽  
Author(s):  
KH Bell
Keyword(s):  
Carbonyl Group ◽  
Absolute Configuration ◽  
Kinetic Resolution ◽  
Optically Active ◽  
Primary Amines ◽  
The Absolute

The reaction between primary amines and cis-1,2,2 trimethylcyclopentane-1,3-dicarboxylic anhydride (3) has been shown to be regioselective for the less hindered carbonyl group. Kinetic resolution was observed when racemic primary amines and the (1R,3S) anhydride (3) were used. Similar stereoselectivity was found in the alternative reaction between racemic (3) and optically active primary amines. In both cases, the absolute configuration of the more reactive enantiomeric amine or anhydride could be correlated with a model (7). The use of (3) is recommended for the prediction of the absolute configurations of racemic and optically active primary amines.

2-Cyano-2-indolylpropanoic acid as a chiral derivatizing agent for the absolute configuration assignment of secondary alcohols and primary amines by 1 H NMR and VCD

2017 ◽  
Vol 28 (6) ◽  
pp. 762-782 ◽  
Author(s):  
Claudia I. Bautista-Hernández ◽  
Nayely Trejo-Carbajal ◽  
Erick A. Zúñiga-Estrada ◽  
Alberto Aristeo-Dominguez ◽  
Myriam Meléndez-Rodríguez ◽  
...  
Keyword(s):  
Absolute Configuration ◽  
Primary Amines ◽  
Secondary Alcohols ◽  
H Nmr ◽  
Configuration Assignment ◽  
Derivatizing Agent ◽  
Chiral Derivatizing Agent ◽  
The Absolute

Assignment of the Absolute Configuration of Monofunctional Compounds by Single Derivatization

2015 ◽  
Author(s):  
Josi M. Seco ◽  
Emilio Quiqoa ◽  
Ricardo Riguera
Keyword(s):  
Absolute Configuration ◽  
Graphical Model ◽  
Chemical Shifts ◽  
Alternative Methods ◽  
Primary Amines ◽  
Secondary Alcohols ◽  
The Absolute ◽  
Lower Temperature

The procedures shown in Chapter 3 allow the determination of the absolute configuration of several classes of compounds (Chapter 1, Figure 1.18), but they require the preparation of two derivatives and the comparison of their NMR spectra. Alternative methods have been developed for secondary alcohols and α-chiral primary amines. These are particularly suited for those cases where the amount of the available sample is low, and they require the preparation of only a single derivative [41–43, 55–56, 165]. There are three different approaches to using only a single derivatization to perform the assignment of those substrates [13, 165]. The first two are based on a controlled conformational change that is produced either by modification of the probe temperature [41, 165] or by selective complexation [42, 55, 56, 165]. The third one is based on the differences observed between the chemical shifts of the free alcohol and those of the 9-AMA ester derivative [43, 165]. In general, these single-derivatization procedures are limited to 1H NMR. Because the shift differences observed in 13C NMR are quite small, they produce insignificant Δδ values, and therefore the signs are not sufficiently accurate to produce a safe assignment [72]. Explanations and examples of applications are presented in the remainder of this chapter. For the assignment of secondary alcohols, a simple approach based on the use of a single MPA ester has proven to work very well [41, 165]. It is based on the controlled shift of the conformational equilibrium between the two main conformers (sp/ap) that were described in Chapter 1 for the MPA esters of secondary alcohols [36, 37]. Thus, for the assignment, it is only necessary to prepare either the (R)- or the (S)-MPA ester and then to compare the chemical shifts of L1/L2 in the spectra taken at room temperature and at a lower temperature [41]. Figure 4.2 presents a summary of the procedure and the graphical model expressing the ΔδT1T2 correlation between the sign and the stereochemistry for the assignment of secondary alcohols derivatized as (R)- or as (S)-MPA esters.

Kinetic resolution of sterically hindered secondary alcohols catalyzed by aminophosphinite organocatalyst

Tetrahedron ◽  
2018 ◽  
Vol 74 (2) ◽  
pp. 296-302 ◽  
Author(s):  
Nanami Hara ◽  
Shu Fujisawa ◽  
Mizuki Fujita ◽  
Mikako Miyazawa ◽  
Kazuma Ochiai ◽  
...  
Keyword(s):  
Kinetic Resolution ◽  
Secondary Alcohols ◽  
Sterically Hindered
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