Stereospecific synthesis of hexahydrobenzopyrroloisoquinoline and tetrahydrobenzisoquinoline derivatives

1984 ◽  
Vol 37 (4) ◽  
pp. 819 ◽  
Author(s):  
E Gellert ◽  
N Kumar
Keyword(s):  
Amino Acids ◽  
Metal Hydride ◽  
Optically Active ◽  
Stereospecific Synthesis ◽  
Hydride Reduction ◽  
The Absolute ◽  
Absolute Stereochemistry

New optically active hexahydrobenzopyrroloisoquinoline and tetrahydrobenzisoquinoline derivatives have been synthesized. Metal hydride reduction of the cyclic amino ketones, prepared by mild Friedel-Crafts type intramolecular acylation of N-naphthalenylmethyl amino acids, yielded pairs of diastereoisomeric alcohols. The absolute stereochemistry and some features of the n.m.r. spectra of hexahydrobenzopyrroloisoquinolines, tetrahydrobenzisoquinoline and those of their intermediates are discussed.

Synthesis of anisomycin. Part I. The stereospecific synthesis of N-benzoyl-2-(p-methoxybenzyl)-3-hydroxy-4-carboxamido pyrrolidine and the absolute configuration of anisomycin

1968 ◽  
Vol 46 (7) ◽  
pp. 1101-1104 ◽  
Author(s):  
C. M. Wong
Keyword(s):  
Infrared Spectra ◽  
Absolute Configuration ◽  
Optical Rotation ◽  
Specific Rotation ◽  
Stereospecific Synthesis ◽  
Specific Optical Rotation ◽  
Synthetic Compound ◽  
The Absolute ◽  
Hydrolysis Of ◽  
Absolute Stereochemistry

L-Tyrosine was converted stereospecifically to N-benzoyl-2-(p-methoxybenzyl)-3-hydroxy-4-cyanopyrrolidine (10) which had a specific optical rotation [Formula: see text]. Anisomycin was converted also to N-benzoyl-2-(p-methoxybenzyl)-3-hydroxy-4-cyanopyrrolidine (16) which had a specific rotation [Formula: see text]. The infrared spectra of the synthetic compound and the derivative of anisomycin were superimposable with each other. This result showed that the absolute configuration of the three asymmetric centers in (10) of synthetic origin were 2S, 3S, 4S, and those in (16) were 2R, 3R, 4R. Thus, anisomycin should have the absolute stereochemistry 2R, 3S, 4S as depicted in the structure (2). Hydrolysis of the hydroxy nitriles (8) and (10) gave an identical amide (3) which should have the absolute stereochemistry 2S, 3S, 4R as shown in structure (3).

Mosher Amides: Determining the Absolute Stereochemistry of Optically-Active Amines

2008 ◽  
Vol 85 (5) ◽  
pp. 698 ◽  
Author(s):  
Damian A. Allen ◽  
Anthony E. Tomaso ◽  
Owen P. Priest ◽  
David F. Hindson ◽  
Jamie L. Hurlburt
Keyword(s):  
Optically Active ◽  
The Absolute ◽  
Absolute Stereochemistry

Terpenoid chemistry. XXI. ( - )-Epingaione, ( - )-Dehydrongaione, ( - )-Dehydroepingaione, and ( - )-Deisopropylngaione, toxic furanoid sesquiterpenoid ketones from Myoporum deserti

1973 ◽  
Vol 26 (2) ◽  
pp. 375 ◽  
Author(s):  
WD Hamilton ◽  
RJ Park ◽  
GJ Perry ◽  
MD Sutherland
Keyword(s):  
Essential Oils ◽  
Optically Active ◽  
Aqueous Alkali ◽  
Liver Pathology ◽  
Liver Lesions ◽  
Literature Report ◽  
The Absolute ◽  
Absolute Stereochemistry

The isolation and properties of four furanoid sesquiterpene ketones from various specimens of the stock-poisoning shrub Myoporum deserti are described. (-)-Epingaione [(-)-(1S,4S)-β-(4,8-dimethyl-6-oxo-1,4- epoxynonyl)furan] may be epimerized to (-)-ngaione either thermally or by base. (-)-Dehydrongaione [(-)-(1S,4R)-β-(4,8-dimethyl-6-oxo-1,4- epoxynon-7-enyl)-furan] is hydrogenated to (-)-ngaione and is equilibrated either thermally or by base with the unconjugated isopropenylic non-8-enyl isomer and (-)-dehydroepingaione [the (1S,4S)- diastereomer], which is hydrogenated to (-)-epingaione. Treatment of dehydrongaione and its epimer with aqueous alkali yields (-)- deisopropylngaione and its epimer by a retroaldol reaction. ��� The argument used by Matsuura1 to deduce the absolute stereochemistry of (+)-ngaione (ipomeamorone) is invalid since, contrary to the literature report, the ipomic lactone obtained from the oxidation of ngaione is not optically active. ��� Specimens of M. deserti have been found which yield essential oils containing each of the four furanoid ketones (-)-ngaione, (-)- epingaione, (-)-dehydrongaione, and (-)-dehydroepingaione free or virtually free from the others. The presence of a few percent of (-)- deisopropylngaione in one (dehydrongaione-rich) M. deserti oil has been demonstrated. ��� (+)-Ngaione, (-)-epingaione, and a mixture of (-)-dehydrongaione and (-)-dehydroepingaione all cause the typical (-)-ngaione liver pathology when injected intraperitoneally into mice. M. deserti plants containing the latter three ketones must be regarded as potentially capable of inducing M. deserti poisoning in stock. A mixture of (-)- deisopropylngaione and (-)- deisopropylepingaione causes both kidney and liver lesions.

Absolute Stereochemistry of (-)-Wieland-Miescher Ketone as Established by the X-ray Crystallographic and CD Exciton Chirality Methods

1992 ◽  
Vol 57 (7) ◽  
pp. 1459-1465 ◽  
Author(s):  
Nobuyuki Harada ◽  
Tatsuo Sugioka ◽  
Hisashi Uda ◽  
Takeo Kuriki
Keyword(s):  
Structure Analysis ◽  
Absolute Configuration ◽  
X Ray ◽  
The Absolute ◽  
Absolute Stereochemistry

The 8aR absolute stereochemistry of Wieland-Miescher ketone (-)-I was established by the X-ray structure analysis of its bis(4-bromobenzoate) derivatives (1R,6R,8aR)-(+)-IV and (1R,6S,8aR)-(-)-V. The absolute configuration of (-)-I was corroborated further by the application of the CD exciton chirality method to bis(4-bromobenzoates) (+)-IV and (-)-V.

scholarly journals Rapid Organocatalytic Chirality Analysis of Amines, Amino Acids, Alcohols, Amino Alcohols and Diols with Achiral Iso(thio)cyanate Probes

2021 ◽  
Author(s):  
Eryn Nelson ◽  
Jeffrey S. S. K. Formen ◽  
Christian Wolf
Keyword(s):  
Amino Acids ◽  
Absolute Configuration ◽  
Rapid Determination ◽  
Amino Alcohols ◽  
Enantioselective Synthesis ◽  
Widespread Occurrence ◽  
Chiral Compounds ◽  
New Methods ◽  
The Absolute

The widespread occurrence and significance of chiral compounds does not only require new methods for their enantioselective synthesis but also efficient tools that allow rapid determination of the absolute configuration,...

Determination of the Absolute Stereochemistry of Cyclosmenospongine

2003 ◽  
Vol 66 (9) ◽  
pp. 1263-1265 ◽  
Author(s):  
Natalia K. Utkina ◽  
Vladimir A. Denisenko ◽  
Olga V. Scholokova ◽  
Aleksandra E. Makarchenko
Keyword(s):  
The Absolute ◽  
Absolute Stereochemistry
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