ChemInform Abstract: STEROIDS. PART XLI. MICHAEL ADDITION OF DIETHYL MALONATE TO STEROIDAL 3-KETO-1,4,6-TRIENES

1979 ◽  
Vol 10 (29) ◽  
Author(s):  
M. KOCOR ◽  
W. KROSZCZYNSKI ◽  
J. PIETRZAK ◽  
T. CYNKOWSKI
Keyword(s):  
Michael Addition ◽  
Diethyl Malonate

Enantioselective Michael Addition: An Experimental Introduction to Asymmetric Synthesis

2019 ◽  
Author(s):  
Martin Tiano
Keyword(s):  
Undergraduate Students ◽  
Michael Addition ◽  
Enantiomeric Excess ◽  
Diethyl Malonate ◽  
2D Nmr ◽  
Shift Reagent ◽  
Experimental Session ◽  
H Nmr ◽  
Asymmetric Michael Addition ◽  
Chiral Lewis Acid

<p> We adapted a classical asymmetric Michael addition for a 1-day experimental session (6-8 hrs) for third or fourth-year undergraduate students. The experiment follows up three steps : synthesis of a chiral Lewis Acid, LiAl(BINOL)<sub>2</sub>, then its use as a catalyst in the Michael addition of diethyl malonate on cyclopentenone, followed by purification through column chromatography on silica gel. The desired product can be fully characterized by 1D and 2D NMR experiments and IR spectroscopy. The enantiomeric excess can be determined by polarimetry and <sup>1</sup>H NMR using chiral lanthanide shift reagent Eu(hfc)<sub>3</sub>.</p>

Asymmetric Synthesis of Adamantyl GABA Analogues

Synthesis ◽  
2018 ◽  
Vol 51 (02) ◽  
pp. 463-469 ◽  
Author(s):  
Anastasiya Sibiryakova ◽  
Vadim Shiryaev ◽  
Alexander Reznikov ◽  
Anastasiya Kabanova ◽  
Yuri Klimochkin
Keyword(s):  
Asymmetric Synthesis ◽  
Michael Addition ◽  
Diethyl Malonate ◽  
Efficient Synthesis ◽  
Synthetic Strategy ◽  
Asymmetric Michael Addition ◽  
Gaba Analogues ◽  
Sterically Hindered

An efficient synthesis of (R)- and (S)-4-amino-3-(adamant-1-yl)butyric acids and (R)- and (S)-4-(adamant-1-yl)pyrrolidin-2-ones is presented. The synthetic strategy is based on asymmetric Michael addition of diethyl malonate to 1-(adamant-1-yl)-2-nitroethene using available Ni(II) complex as the catalyst. The procedures provide good to high enantioselectivity of Michael addition to sterically hindered nitroalkene and good yields of (R)- and (S)-enantiomers of 3-adamantyl substituted GABA.

TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART VI. STEREOCHEMISTRY OF THE MICHAEL ADDITION OF ETHYL MALONATE TO 1-CYCLOHEXENE CYANIDE

1960 ◽  
Vol 38 (4) ◽  
pp. 557-566 ◽  
Author(s):  
R. A. Abramovitch ◽  
J. M. Muchowski
Keyword(s):  
Michael Addition ◽  
Diethyl Malonate ◽  
Aminomethyl Derivative ◽  
Fischer Cyclization ◽  
Ethyl Malonate ◽  
Cis And Trans ◽  
Related Compounds ◽  
The Michael Addition

The Michael addition of diethyl malonate to 1-cyclohexene cyanide has been shown to give a mixture of the cis- and trans-diethyl 2-cyanocyclohexylmalonates in 72% and 28% yields respectively. The stereochemistry of the products was established by their unambiguous conversion to the respective cis- and trans-decahydroisoquinolines. Hydrogenation of a cyclohexane cyanide to the corresponding aminomethyl derivative takes place with retention of configuration. A number of substituted decahydroisoquinolines of known stereochemistry have been prepared. Decahydro-3,4-dioxoisoquinoline-4-phenylhydrazone underwent Fischer cyclization to a product assumed to be 2-oxo-octahydroindolo[2,3-d]isoquinoline indicating that the observation that 4-methyl-2,3-dioxopiperidine-3-phenylhydrazone did not undergo cyclization is not general for such 4-substituted piperidones.

Condensation reactions of 1,1-dimorpholinoethene and of 1,1-dipiperidinoethene with carbon acids

1987 ◽  
Vol 65 (12) ◽  
pp. 2717-2721 ◽  
Author(s):  
Sham S. Gandhi ◽  
Martin S. Gibson
Keyword(s):  
Michael Addition ◽  
Ethyl Acetoacetate ◽  
Ethyl Cyanoacetate ◽  
Diethyl Malonate ◽  
Condensation Reactions ◽  
Acetyl Group ◽  
Carbon Acids

1,1-Dimorpholinoethene and 1,1-dipiperidinoethene condense with such compounds as malononitrile, ethyl cyanoacetate, cyanoacetamide, and diethyl malonate to give the corresponding β,β-disubstituted enamine, a molecule of morpholine or piperidine being eliminated in the process. Similar reactions with acetylacetone and ethyl acetoacetate proceed with loss of the acetyl group to give the β-substituted enamine. 1,1-Dipiperidinoethene and nitromethane give the β-nitroenamine. Secondary processes of either hydrolysis or further Michael addition and elimination are noted in condensations of 1,1-dimorpholinoethene or 1,1-dipiperidinoethene with cyanoacetamide under more basic conditions.1,1-Dipiperidinoethene is arylated at the 2-position by 2,4-dinitrochlorobenzene.

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