scholarly journals General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides and Lactams

ACS Catalysis ◽  
2021 ◽  
pp. 7489-7497
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Azomethine Ylide ◽  
Tertiary Amides

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

scholarly journals A General Pyrrolidine Synthesis via Iridium-Catalyzed Reductive Azomethine Ylide Generation from Tertiary Amides & Lactams

2021 ◽  
Author(s):  
Ken Yamazaki ◽  
Pablo Gabriel ◽  
Graziano Di Carmine ◽  
Julia Pedroni ◽  
Mirxan Farizyan ◽  
...  
Keyword(s):  
Density Functional ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Cycloaddition Reactions ◽  
Reaction Conditions ◽  
Functional Theory ◽  
Efficient Access ◽  
Stabilized Azomethine Ylides ◽  
Tertiary Amides

A new iridium-catalyzed reductive generation of both stabilized and unstabilized azomethine ylides and their application to functionalized pyrrolidine synthesis via [3+2] dipolar cycloaddition reactions is described. Proceeding under mild reaction conditions from both amide and lactam precursors possessing a suitably positioned electron-withdrawing or a trimethylsilyl group, using catalytic Vaska’s complex [IrCl(CO)(PPh3)2] and tetramethyldisiloxane (TMDS) as a terminal reductant, a broad range of (un)stabilized azomethine ylides were accessible. Subsequent, regio- and diastereoselective, inter- and intramolecular, dipolar cycloaddition reactions with variously substituted electron-poor alkenes enabled ready and efficient access to structurally complex pyrrolidine architectures. Density functional theory (DFT) calculations of the dipolar cycloaddition reactions uncovered an intimate balance between asynchronicity and interaction energies of transition structures which ultimately control the unusual selectivities observed in certain cases.

Reactions of 4-Pyrones with Azomethine Ylides as a Chemo­selective Method for the Construction of Multisubstituted Pyrano[2,3-c]pyrrolidines

Synthesis ◽  
2021 ◽  
Author(s):  
Dmitrii L. Obydennov ◽  
Vyacheslav D. Steben’kov ◽  
Konstantin L. Obydennov ◽  
Sergey A. Usachev ◽  
Vladimir S. Moshkin ◽  
...  
Keyword(s):  
Double Bond ◽  
Ring Opening ◽  
Azomethine Ylides ◽  
Azomethine Ylide ◽  
Dipolar Cycloaddition ◽  
Computational Studies ◽  
Carbon Double Bond ◽  
Reactivity Indexes ◽  
Reaction Proceeds

Abstract4-Pyrones bearing electron-donating and electron-withdrawing groups react with nonstabilized azomethine ylides to form pyrano[2,3-c]pyrrolidines in moderate to good yields. The reaction proceeds chemoselectively as a 1,3-dipolar cycloaddition of the azomethine ylide at the carbon–carbon double bond of the pyrone activated by the electron-withdrawing substituent. The reactivity of 4-pyrones toward azomethine ylides was rationalized by computational studies with the use of reactivity indexes. The pyrano[2,3-c]pyrrolidine moiety could be modified, for example by a ring-opening transformation under the action of hydrazine to provide pyrazolyl-substituted pyrrolidines.

scholarly journals Shedding Light on the Chemistry and the Properties of Münchnone Functionalized Graphene

Nanomaterials ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 1629
Author(s):  
Giulia Neri ◽  
Enza Fazio ◽  
Antonia Nostro ◽  
Placido Giuseppe Mineo ◽  
Angela Scala ◽  
...  
Keyword(s):  
Density Functional ◽  
Antimicrobial Properties ◽  
Biological Properties ◽  
Azomethine Ylide ◽  
Functionalized Graphene ◽  
Functional Theory ◽  
Pyrrole Derivatives ◽  
Transmission Electron ◽  
Scanning Transmission ◽  
Direct Functionalization

Münchnones are mesoionic oxazolium 5-oxides with azomethine ylide characteristics that provide pyrrole derivatives by a 1,3-dipolar cycloaddition (1,3-DC) reaction with acetylenic dipolarophiles. Their reactivity was widely exploited for the synthesis of small molecules, but it was not yet investigated for the functionalization of graphene-based materials. Herein, we report our results on the preparation of münchnone functionalized graphene via cycloaddition reactions, followed by the spontaneous loss of carbon dioxide and its further chemical modification to silver/nisin nanocomposites to confer biological properties. A direct functionalization of graphite flakes into few-layers graphene decorated with pyrrole rings on the layer edge was achieved. The success of functionalization was confirmed by micro-Raman and X-ray photoelectron spectroscopies, scanning transmission electron microscopy, and thermogravimetric analysis. The 1,3-DC reactions of münchnone dipole with graphene have been investigated using density functional theory to model graphene. Finally, we explored the reactivity and the processability of münchnone functionalized graphene to produce enriched nano biomaterials endowed with antimicrobial properties.

Five-Step Total Synthesis of (±)-Aspidospermidine by a Lactam Strategy via an Azomethine Ylide

2021 ◽  
Vol 23 (8) ◽  
pp. 3058-3063
Author(s):  
Seiya Katahara ◽  
Yasukazu Sugiyama ◽  
Mina Yamane ◽  
Yukinori Komiya ◽  
Takaaki Sato ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Azomethine Ylide

Lithium compound catalyzed deoxygenative hydroboration of primary, secondary and tertiary amides

2021 ◽  
Vol 50 (7) ◽  
pp. 2354-2358
Author(s):  
Milan Kumar Bisai ◽  
Kritika Gour ◽  
Tamal Das ◽  
Kumar Vanka ◽  
Sakya S. Sen
Keyword(s):  
Lithium Compound ◽  
Tertiary Amides

A very simple and readily accessible lithium compound has been employed to catalyze the hydroboration of tertiary, secondary, and primary amides to the corresponding amines.

Bromination of Enamines from Tertiary Amides Using the Petasis Reagent: A Convenient One-Pot Regioselective Route to Bromomethyl Ketones

2013 ◽  
Vol 43 (21) ◽  
pp. 2955-2965 ◽  
Author(s):  
Marwan Kobeissi ◽  
Khalil Cherry ◽  
Wissam Jomaa
Keyword(s):  
One Pot ◽  
Tertiary Amides
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