scholarly journals The Use of UiO-Type MOFs in Vapour Phase Soai Reactions

2020 ◽  
Author(s):  
Giuesppe rotunno ◽  
Gurpreet Kaur ◽  
Andrea Lazzarini ◽  
Carlo Buono ◽  
Mohamed Amedjkouh
Keyword(s):  
Asymmetric Synthesis ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Vapour Phase ◽  
Absolute Asymmetric Synthesis ◽  
Soai Reaction

We report a novel vapour phase procedure to perform the Soai reaction in an absolute asymmetric synthesis fashion: the substrate is confined in the pores of the UiO-type MOFs, and vapour phase reactions with Zn(i-Pr)<sub>2</sub> are performed in a sealed environment, Different MOFs lead to different outcomes in terms of enantiomeric excess, handedness of the product and reaction rate. This is one of the first examples of absolute asymmetric synthesis performed inside a MOF.

scholarly journals The Use of UiO-Type MOFs in Vapour Phase Soai Reactions

2020 ◽  
Author(s):  
Giuesppe rotunno ◽  
Gurpreet Kaur ◽  
Andrea Lazzarini ◽  
Carlo Buono ◽  
Mohamed Amedjkouh
Keyword(s):  
Asymmetric Synthesis ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Vapour Phase ◽  
Absolute Asymmetric Synthesis ◽  
Soai Reaction

We report a novel vapour phase procedure to perform the Soai reaction in an absolute asymmetric synthesis fashion: the substrate is confined in the pores of the UiO-type MOFs, and vapour phase reactions with Zn(i-Pr)<sub>2</sub> are performed in a sealed environment, Different MOFs lead to different outcomes in terms of enantiomeric excess, handedness of the product and reaction rate. This is one of the first examples of absolute asymmetric synthesis performed inside a MOF.

Absolute Asymmetric Synthesis: A Commentary

2003 ◽  
Vol 68 (5) ◽  
pp. 849-864 ◽  
Author(s):  
Kurt Mislow
Keyword(s):  
Asymmetric Synthesis ◽  
Enantiomeric Excess ◽  
Optically Active ◽  
Random Chance ◽  
Chemical Reagents ◽  
Absolute Asymmetric Synthesis ◽  
Asymmetric Autocatalysis ◽  
Physical Forces ◽  
Biomolecular Homochirality ◽  
The Difference

Absolute asymmetric synthesis, i.e., the formation of enantiomerically enriched products from achiral precursors without the intervention of chiral chemical reagents or catalysts, is in practice unavoidable on statistical grounds alone. That random chance, combined with suitable amplification mechanisms, might ultimately account for biomolecular homochirality in Nature was recognized more than a century ago. Soai and collaborators have recently developed an asymmetric autocatalysis reaction that is capable of amplifying a tiny enantiomeric excess of far below 1% to yield a nearly enantiopure product. Although there is no easy way to tell the difference between an asymmetric autocatalysis reaction initiated by the tiny enantiomeric excess due to random chance and one initiated by minuscule quantities of unidentified chiral impurities, it is nevertheless all but certain that the Soai reaction is capable of producing optically active compounds by an absolute asymmetric synthesis, starting from nominally achiral reagents free of chiral contaminants and run under achiral conditions, e.g., without the intervention of chiral physical forces.

Chemistry of Fenchonesulfonic Acid Derivatives

1995 ◽  
Vol 50 (2) ◽  
pp. 283-288 ◽  
Author(s):  
Gabriele Wagner ◽  
Uwe Verfürth ◽  
Rudolf Herrmann
Keyword(s):  
Acetic Anhydride ◽  
Thionyl Chloride ◽  
Sulfonic Acid ◽  
Reaction Rate ◽  
Enantiomeric Excess ◽  
Methyl Group ◽  
Close Analogy ◽  
Chiral Sulfoxides ◽  
Mndo Calculations ◽  
Nmr Techniques

(1 S) - (+)-Fenchone is sulfonated by SO3 or H2SO4/acetic anhydride in the bridgehead methyl group. This could be confirmed by NMR techniques (INADEQUATE). The fenchonesulfonic acid obtained is converted (SOCl2/NH3) to the cyclic fenchonesulfonimide, which can be oxidized to the corresponding oxaziridine, in close analogy to 10-camphorsulfonimide. Improved procedures for this reaction sequences are given. During the treatment of the sulfonic acid with thionyl chloride, a byproduct with a rearranged bicyclic skeleton is observed whose structure has been determined by ozonolytic degradation and NMR techniques. A possible mechanism for this rearrangement is suggested, based on MNDO calculations of the intermediate carbocations. The fenchonesulfonyloxaziridine oxidizes sulfides to chiral sulfoxides with appreciable enantiomeric excess, but very low reaction rate. A comparison with camphor-derived oxaziridines having similar steric requirements is made.

Absolute Asymmetric Synthesis of Tertiary α-Amino Acids

2012 ◽  
Vol 124 (20) ◽  
pp. 5065-5068 ◽  
Author(s):  
Thi Thoa Mai ◽  
Mathieu Branca ◽  
Didier Gori ◽  
Régis Guillot ◽  
Cyrille Kouklovsky ◽  
...  
Keyword(s):  
Amino Acids ◽  
Asymmetric Synthesis ◽  
Absolute Asymmetric Synthesis

Asymmetric synthesis of new γ-butenolides via organocatalyzed epoxidation of chalcones

2017 ◽  
Vol 15 (29) ◽  
pp. 6098-6103 ◽  
Author(s):  
Lucas C. C. Vieira ◽  
Bianca T. Matsuo ◽  
Lorena S. R. Martelli ◽  
Mayara Gall ◽  
Marcio W. Paixão ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
Enantiomeric Excess ◽  
Chromatographic Purification

A greener three-step sequence, with only one single chromatographic purification, afforded γ-butenolides in moderate overall yield and high enantiomeric excess.

Asymmetric Synthesis of Chiral Tertiary Alcohols in High Enantiomeric Excess

1982 ◽  
pp. 37-53 ◽  
Author(s):  
ERNEST L. ELIEL ◽  
JORMA K. KOSKIMIES ◽  
BRUNO LOHRI ◽  
W. JACK FRAZEE ◽  
SUSAN MORRIS-NATSCHKE ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
Enantiomeric Excess ◽  
Tertiary Alcohols ◽  
Chiral Tertiary Alcohols
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