Copper/GanPhos-Catalyzed 1,3-Dipolar Cycloaddition of Azo­methine Ylides: An Efficient Access to Chiral Pyrrolidine Spirocycles

Synthesis ◽  
2020 ◽  
Author(s):  
Zhenjie Gan ◽  
Er-Qing Li ◽  
Ke Li ◽  
Hui Zhang
Keyword(s):  
Optically Active ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Reaction Conditions ◽  
Highly Efficient ◽  
Efficient Access ◽  
Stereogenic Centers

AbstractA highly efficient copper/GanPhos-catalyzed 1,3-dipolar cyclo­addition­ of azomethine ylides is reported. This viable transformation provides a series of optically active spiro[dihydronaphthalene-2,3′-pyrrolidine]s, bearing one spiro quaternary and three tertiary stereogenic centers, in good yields and with high ee values. This protocol features high diastereo- and enantioselectivity, broad substrate scope and mild reaction conditions.

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 Highly Efficient and Diastereoselective Construction of Substituted Pyrrolidines Bearing A Quaternary Carbon Center via 1,3-Dipolar [3 + 2] Cycloaddition

2021 ◽  
Author(s):  
Kaikai wang ◽  
Yanli Li ◽  
Yingchao Zhao ◽  
Aili sun ◽  
Rongxiang Chen ◽  
...  
Keyword(s):  
Efficient Method ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Quaternary Carbon ◽  
Reaction Conditions ◽  
Highly Efficient ◽  
High Yields

A general approach to substituted pyrrolidines via [3 + 2] 1,3-dipolar cycloaddition between nonstabilized azomethine ylides and cyanosulfones was developed. The efficient method provides a series of substituted pyrrolidines bearing a quaternary carbon center in high yields (up to 98%) excellent diastereoselectivities (up to >25:1 dr) under ambient reaction conditions.

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.

Organocatalytic synthesis of chiral CF3-containing oxazolidines and 1,2-amino alcohols: asymmetric oxa-1,3-dipolar cycloaddition of trifluoroethylamine-derived azomethine ylides

2020 ◽  
Vol 7 (21) ◽  
pp. 3452-3458
Author(s):  
Wen-Run Zhu ◽  
Qiong Su ◽  
Ning Lin ◽  
Qing Chen ◽  
Zhen-Wei Zhang ◽  
...  
Keyword(s):  
Amino Alcohols ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Stereogenic Centers

A series of CF3-containing oxazolidines were constructed via organocatalytic asymmetric oxa-1,3-dipolar cycloaddition. These oxazolidines could undergo facile conversion to CF3-containing 1,2-amino alcohols with vicinal stereogenic centers.

scholarly journals Synthesis of polysubstituted spiropyrrolidines using 2-acetylfuran, 2-acetylthiophene, and 2-acetylpyrrole

2021 ◽  
Vol 21 (3) ◽  
pp. 254-259
Author(s):  
Svetlana V. Borisova ◽  
◽  
Vitaly V. Sorokin ◽  
Keyword(s):  
13C Nmr Spectroscopy ◽  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Knoevenagel Reaction ◽  
Atom Economy ◽  
Reaction Conditions ◽  
Stereo Selectivity ◽  
Decarboxylative Condensation ◽  
First Time

A series of novel spirooxindoles have been synthesized through three-component 1,3-dipolar cycloaddition of azomethine ylides generated in situ by the decarboxylative condensation of isatin and sarcosine with the dipolarophile 3-phenyl-1-(heteroaryl -2-yl)prop-2-en-1- one, synthesized by the Knoevenagel reaction using 2-acetylfuran, 2-acetylpyrrole, 2-acetylthiophene and substituted benzaldehydes. These compounds are used for the first time as dipolarophiles. This method has the advantages of mild reaction conditions, high atom economy, excellent yields, and high regio- and stereo-selectivity. The reaction was carried out by mixing equimolar amounts of enone and isatin, as well as a slight excess of sarcosine in isopropyl alcohol when heated to 60–70°C. Among the enones with various heterocyclic substituents, it is most convenient to use compounds containing a pyrrole fragment as dipolarophiles, since the products are obtained in a short amount of time in good yields. The use of enones obtained from 2-acetylthiophene leads to an increase in the reaction time, and from 2-acetylfuran - to a significant resinification of the reaction mixture. The structures of the compounds obtained were proved using a combination of 1H, 13C NMR spectroscopy data, as well as two-dimensional NMR experiments of heteronuclear correlation, HSQC and HMBC. Based on the data obtained, a mechanism for the formation of products has been proposed.

Highly efficient desymmetrization of cyclopropenes to azabicyclo[3.1.0]hexanes with five continuous stereogenic centers by copper-catalyzed [3 + 2] cycloadditions

2018 ◽  
Vol 5 (18) ◽  
pp. 2759-2764 ◽  
Author(s):  
Yang Yuan ◽  
Zhan-Jiang Zheng ◽  
Fei Ye ◽  
Jun-Han Ma ◽  
Zheng Xu ◽  
...  
Keyword(s):  
Cycloaddition Reaction ◽  
Highly Efficient ◽  
Efficient Access ◽  
Stereogenic Centers

An unprecedented copper-catalyzed desymmetrization/cycloaddition reaction of 1,1-disubstituted cyclopropenes provides an efficient access to azabicyclo[3.1.0]hexanes bearing five continuous carbon-stereogenic centers.

Copper(i)-catalyzed asymmetric exo-selective [3+2] cycloaddition of azomethine ylides with β-trifluoromethyl β,β-disubstituted enones

2017 ◽  
Vol 53 (58) ◽  
pp. 8152-8155 ◽  
Author(s):  
Bing Xu ◽  
Zhan-Ming Zhang ◽  
Bing Liu ◽  
Shan Xu ◽  
Lu-Jia Zhou ◽  
...  
Keyword(s):  
Azomethine Ylides ◽  
Dipolar Cycloaddition ◽  
Efficient Access ◽  
Quaternary Stereocenter

A copper-catalyzed asymmetricexo-selective dipolar cycloaddition of β-trifluoromethyl β,β-disubstituted enones with azomethine ylides was developed, which provides an efficient access to valuable pyrrolidines bearing a trifluoromethylated all-carbon quaternary stereocenter.

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