Elucidation of the absolute configurations of amino acids and amines by the modified mosher's method

Kusumi, Takenori; Fukushima, Toshiro; Ohtani, Ikuko I.; Kakisawa, Hiroshi

doi:10.1016/0040-4039(91)80655-p

Cited by 141 publications

(73 citation statements)

References 9 publications

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“…5 This method is also applicable to amines and amino acids. 6 Additionally, a variety of modified derivatizing reagents, chiral anisotropic reagents, have been recently developed, which made it possible to determine the absolute configurations of various chiral carboxylic acids as well as secondary alcohols. 7À9 Essentially the same method using O-methylmandelic acid and the related arylmethoxyacetate have been reported.…”

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confidence: 99%

Determination of absolute configuration of 1,3‐diols by the modified Mosher's method using their di‐MTPA esters

et al. 2001

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1,3-Diols are frequently involved in biologically important compounds and, therefore, determination of the stereochemistry of these structural elements, in particular those in acyclic systems, has been one of the focuses of attention in natural products chemistry. The modified Mosher's method, commonly used for the determination of the absolute configuration of secondary alcohols, was applied to determine the absolute configuration of 1,3-diols with their di-MTPA esters. Several epimeric pairs of syn- and anti-1,3-diols with known absolute configurations were converted to the corresponding di-MTPA esters and the iDelta;delta values were then calculated. For the acyclic syn-1,3-diols, the iDelta;delta values were systematically arranged as predicted from the basic concept of the modified Mosher's method, demonstrating that the method is valid for these compounds. In contrast, the iDelta;delta values were irregularly arranged for the acyclic anti-1,3-diols and, accordingly, this method is not valid for these cases. These results are complementary to those of the previously reported CD exciton chirality method and, hence, the combined use of the modified Mosher's method and the CD exciton chirality method can determine the absolute configuration of the acyclic 1,3-diols. Also, this method is successfully applicable to cyclic 1,3-diols irrespective of their relative stereochemistry.

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confidence: 99%

Determination of absolute configuration of 1,3‐diols by the modified Mosher's method using their di‐MTPA esters

et al. 2001

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“…In this regard, we focused out attention on NMR methods for the determination of the absolute configuration of chiral primary amines. [40] These methods usually involve a double derivatization of the substrate of unknown configuration with the two enantiomers of a chiral auxiliary. Then the chemical shifts of the signals due to protons in the resulting diastereoisomers are determined and the corresponding differences expressed as Dd RS .…”

Section: Resultsmentioning

confidence: 99%

Multiple Component Approaches to C‐Glycosyl β‐Amino Acids by Complementary One‐Pot Mannich‐Type and Reformatsky‐Type Reactions

Dondoni

Massi

Sabbatini

2005

Chemistry A European J

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The development of new methods for the preparation of C-glycosyl beta-amino acid libraries with chemical and stereochemical diversity levels was investigated and the results are described herein. Two complementary one-pot three-component Mannich-type and Reformatsky-type synthetic strategies have been developed for the construction of chiral 3-amino propanoate fragments (eventually bis-substituted at C-2) directly linked to the anomeric carbon of pyranose and furanose residues. Both methods involved as the initial step the coupling of a sugar aldehyde to p-methoxybenzylamine but differed in the nucleophile (a d(2) synthon equivalent) which was successively added: a ketene silyl acetal (Mannich route) or a bromozinc enolate (Reformatsky route). Individual C-glycosyl beta-amino esters were isolated as single 3R diastereoisomers in fair to excellent yield (60-90%) and their structure assigned by NMR spectroscopy (Riguera protocol) supported by X-ray crystallography. A tentative explanation of the observed stereochemical outcome based on transition-state models is provided. A preliminary study on the synthesis of alpha,alpha-difluoro C-glycosyl beta-amino acids via a more traditional Reformatsky route is also reported.

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“…The absolute stereochemistry of the formed stereogenic center in 57 was determined by analysis of the MTPA amides 59 by using Kusumi's method for elucidation of the absolute configuration of primary amines. 26) The mechanistic investigations demonstrated that the allyl cyanate-to-isocyanate rearrangement is a concerted [3.3] sigmatropic process involving highly selective [1,3]-chirality transfer to the newly formed asymmetric, nitrogen-bearing center.…”

Section: The Stereochemistry and Mechanism Of The Allyl Cyanate-to-ismentioning

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Evolution, Development and Personal Experience in Studies of the Allyl Cyanate-to-Isocyanate Rearrangement

Ichikawa¹

2007

Synlett

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Evolution and development of the synthesis and rearrangement of allyl cyanate is described. Allyl cyanate-to-isocyanate rearrangement is a concerted [3.3]-sigmatropic process involving highly selective [1,3]-chirality transfer to the newly formed asymmetric center bearing nitrogen. The usefulness of this rearrangement is manifested by the synthesis of natural products containing nitrogen-substituted quaternary carbon atoms. 1 Background 2 Evolution of the Allyl Cyanate-to-Isocyanate Rearrangement. A Personal History 3 The Stereochemistry and Mechanism of the Allyl Cyanateto-Isocyanate Rearrangement 4 Synthesis of Natural Products Containing Nitrogen-Substituted Quaternary Carbon Centers 5 Coda

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Elucidation of the absolute configurations of amino acids and amines by the modified mosher's method

Cited by 141 publications

References 9 publications

Determination of absolute configuration of 1,3‐diols by the modified Mosher's method using their di‐MTPA esters

Determination of absolute configuration of 1,3‐diols by the modified Mosher's method using their di‐MTPA esters

Multiple Component Approaches to C‐Glycosyl β‐Amino Acids by Complementary One‐Pot Mannich‐Type and Reformatsky‐Type Reactions

Evolution, Development and Personal Experience in Studies of the Allyl Cyanate-to-Isocyanate Rearrangement

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