Chiral Tetrahydropyridines via FeCl3-Catalyzed Carbonyl-Olefin Metathesis

10.26434/chemrxiv.10007291 ◽

2019 ◽

Author(s):

Katie Rykaczewski ◽

Emilia J. Groso ◽

Hannah L. Vonesh ◽

Mario Gaviria ◽

Alistair D. Richardson ◽

...

Keyword(s):

Amino Acids ◽

Lewis Acid ◽

Olefin Metathesis ◽

Unnatural Amino Acids ◽

Environmentally Benign ◽

Reaction Conditions ◽

Reaction Proceeds ◽

Acid Catalyzed

<div> <div> <p>Herein, we describe the application of Lewis acid-catalyzed carbonyl-olefin metathesis towards the synthesis of chiral, substituted tetrahydropyridines from commercially available amino acids as chiral pool reagents. This strategy relies on FeCl<sub>3</sub> as an inexpensive and environmentally benign catalyst and enables access to a variety of substituted tetrahydropyridines under mild reaction conditions. The reaction proceeds with complete stereoretention and is viable for a variety of natural and unnatural amino acids to provide the corresponding tetrahydropyridines in up to 99% yield.</p> </div> </div> <br>

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Catalytic Carbonyl-Olefin Metathesis of Aliphatic Ketones: Iron(III) HomoDimers as Lewis Acidic Superelectrophiles

10.26434/chemrxiv.7130801.v1 ◽

2018 ◽

Author(s):

Haley Albright ◽

Paul S. Riehl ◽

Christopher C. McAtee ◽

Jolene P. Reid ◽

Jacob R. Ludwig ◽

...

Keyword(s):

Lewis Acid ◽

Olefin Metathesis ◽

Acid Activation ◽

Lewis Acid Catalysts ◽

Distinct Mode ◽

Aliphatic Ketones ◽

Carbon Carbon Bond ◽

Metathesis Reactions ◽

Acid Catalyzed

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in situ formation of a homobimetallic singly-bridged iron(III)-dimer as the active catalytic species. These “superelectrophiles” function as more powerful Lewis acid catalysts that form upon association of individual iron(III)-monomers. While this mode of Lewis acid activation has previously been postulated to exist, it has not yet been applied in a catalytic setting. The insights presented are expected to enable further advancement in Lewis acid catalysis by building upon the activation principle of “superelectrophiles” and broaden the current scope of catalytic carbonyl-olefin metathesis reactions.</div>

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Naturally Occurring Organic Acid-catalyzed Facile Diastereoselective Synthesis of Biologically Active (E)-3-(arylimino)indolin-2-one Derivatives in Water at Room Temperature

Current Organic Chemistry ◽

10.2174/1385272822666190924182538 ◽

2019 ◽

Vol 23 (16) ◽

pp. 1778-1788 ◽

Cited By ~ 5

Author(s):

Gurpreet Kaur ◽

Arvind Singh ◽

Kiran Bala ◽

Mamta Devi ◽

Anjana Kumari ◽

...

Keyword(s):

Room Temperature ◽

Biologically Active ◽

Environmentally Benign ◽

Diastereoselective Synthesis ◽

Substituted Anilines ◽

Reaction Conditions ◽

Naturally Occurring ◽

Acid Catalyzed ◽

Reaction Media ◽

Column Chromatographic

A simple, straightforward and efficient method has been developed for the synthesis of (E)-3-(arylimino)indolin-2-one derivatives and (E)-2-((4-methoxyphenyl)imino)- acenaphthylen-1(2H)-one. The synthesis of these biologically-significant scaffolds was achieved from the reactions of various substituted anilines and isatins or acenaphthaquinone, respectively, using commercially available, environmentally benign and naturally occurring organic acids such as mandelic acid or itaconic acid as catalyst in aqueous medium at room temperature. Mild reaction conditions, energy efficiency, good to excellent yields, environmentally benign conditions, easy isolation of products, no need of column chromatographic separation and the reusability of reaction media are some of the significant features of the present protocol.

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Lewis Acid Catalyzed Intramolecular Allylic Substitution of Bis(trichloroacetimidates): A Versatile Approach to Racemic Unsaturated Amino Acids

European Journal of Organic Chemistry ◽

10.1002/ejoc.201100060 ◽

2011 ◽

Vol 2011 (13) ◽

pp. 2421-2425 ◽

Cited By ~ 20

Author(s):

Liene Grigorjeva ◽

Aigars Jirgensons

Keyword(s):

Amino Acids ◽

Lewis Acid ◽

Allylic Substitution ◽

Acid Catalyzed ◽

Unsaturated Amino Acids

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Critical role of Bronsted acid in Lewis-acid-catalyzed synthesis of Amadori and Heyns compounds of β-amino acids

Synthetic Communications ◽

10.1080/00397911.2021.1971718 ◽

2021 ◽

pp. 1-11

Author(s):

Debasree Chanda ◽

Gangothri M. Venkataswamy ◽

Lagamawwa V. Hipparagi ◽

Nanishankar V. Harohally

Keyword(s):

Amino Acids ◽

Lewis Acid ◽

Critical Role ◽

Bronsted Acid ◽

Brønsted Acid ◽

Brönsted Acid ◽

Acid Catalyzed

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Morpholin-2-one Derivatives via Intramolecular Acid-Catalyzed Hydroamination

Synthesis ◽

10.1055/s-0037-1610674 ◽

2019 ◽

Vol 51 (07) ◽

pp. 1643-1648 ◽

Cited By ~ 1

Author(s):

David Knight ◽

Thomas Wirth ◽

Abdul Hadi Aldmairi

Keyword(s):

Amino Acids ◽

Catalytic Amount ◽

Practical Method ◽

Trifluoromethanesulfonic Acid ◽

Reaction Conditions ◽

Available N ◽

Metal Free ◽

Acid Catalyzed

Substituted morpholin-2-one derivatives were readily obtained in two steps starting from commercially available N-protected amino acids. In a metal-free and practical method, a catalytic amount of trifluoromethanesulfonic acid was sufficient to generate morpholinones under mild reaction conditions in an intramolecular hydroamination reaction in good to excellent yields.

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Lewis Acid-Catalyzed Carbonyl–Olefin Metathesis

Trends in Chemistry ◽

10.1016/j.trechm.2019.02.011 ◽

2019 ◽

Vol 1 (2) ◽

pp. 272-273 ◽

Cited By ~ 2

Author(s):

Paul S. Riehl ◽

Corinna S. Schindler

Keyword(s):

Lewis Acid ◽

Olefin Metathesis ◽

Acid Catalyzed

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A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines

Chemical Communications ◽

10.1039/c8cc01436a ◽

2018 ◽

Vol 54 (28) ◽

pp. 3516-3519 ◽

Cited By ~ 20

Author(s):

Rajshekhar A. Unhale ◽

Milon M. Sadhu ◽

Sumit K. Ray ◽

Rayhan G. Biswas ◽

Vinod K. Singh

Keyword(s):

Phosphoric Acid ◽

Reaction Conditions ◽

Type Reaction ◽

Chiral Phosphoric Acid ◽

Brönsted Acid ◽

Diazo Esters ◽

Reaction Proceeds ◽

Acid Catalyzed ◽

Chiral Bronsted Acid

A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-aryl-3-hydroxyisoindolinones has been demonstrated. The reaction proceeds smoothly under mild reaction conditions.

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