scholarly journals Enantiomerically enriched tetrahydropyridine allyl chlorides

2020 ◽  
Vol 11 (16) ◽  
pp. 4125-4130
Author(s):  
Sedef Karabiyikoglu ◽  
Alexandre V. Brethomé ◽  
Thomas Palacin ◽  
Robert S. Paton ◽  
Stephen P. Fletcher
Keyword(s):  
Kinetic Resolution ◽  
Allyl Chloride ◽  
Catalyst Free ◽  
Allyl Halides

Enantiomerically enriched allyl halides are rare due to their configurational lability. Stable piperidine-based allyl chloride enantiomers can be produced via kinetic resolution, and undergo highly enantiospecific catalyst-free substitutions.

scholarly journals Enantiomerically Enriched Tetrahydropyridine Allyl Chlorides

2019 ◽  
Author(s):  
Sedef Karabiyikoglu ◽  
Alexandre Brethomé ◽  
Thomas Palacin ◽  
Robert Paton ◽  
Stephen P. Fletcher
Keyword(s):  
Dft Calculations ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Allyl Chloride ◽  
Reaction Pathways ◽  
Substitution Reactions ◽  
Catalyst Free ◽  
Kinetic Isotope ◽  
Allyl Halides ◽  
Stereoselective Reaction

Enantiomerically enriched allyl halides are rare due to their configurational lability. Here we report stable piperidine-based allyl chloride enantiomers. These allyl chlorides can be produced via resolution, and undergo highly enantiospecific catalyst-free substitution reactions with C, N, O and S-based nucleophiles. Deuterium-labelled chloro-tetrahydropyridine, selectively prepared using the H/D primary kinetic isotope effect, and DFT calculations were used to investigate the mechanisms of the reactions. The allyl chlorides may also serve as valuable mechanistic tools for probing stereoselective reaction pathways.

scholarly journals Enantiomerically Enriched Tetrahydropyridine Allyl Chlorides

2019 ◽  
Author(s):  
Sedef Karabiyikoglu ◽  
Alexandre Brethomé ◽  
Thomas Palacin ◽  
Robert Paton ◽  
Stephen P. Fletcher
Keyword(s):  
Dft Calculations ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Allyl Chloride ◽  
Reaction Pathways ◽  
Substitution Reactions ◽  
Catalyst Free ◽  
Kinetic Isotope ◽  
Allyl Halides ◽  
Stereoselective Reaction

Enantiomerically enriched allyl halides are rare due to their configurational lability. Here we report stable piperidine-based allyl chloride enantiomers. These allyl chlorides can be produced via resolution, and undergo highly enantiospecific catalyst-free substitution reactions with C, N, O and S-based nucleophiles. Deuterium-labelled chloro-tetrahydropyridine, selectively prepared using the H/D primary kinetic isotope effect, and DFT calculations were used to investigate the mechanisms of the reactions. The allyl chlorides may also serve as valuable mechanistic tools for probing stereoselective reaction pathways.

scholarly journals Highly Enantioselective Hiyama Cross-Coupling via Rh-Catalyzed Allylic Arylation of Racemic Allyl Chlorides

2018 ◽  
Author(s):  
Jesus Gonzalez ◽  
Philipp Schäfer ◽  
Stephen P. Fletcher
Keyword(s):  
Allyl Chloride ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Asymmetric Transformations ◽  
Cross Coupling Reactions ◽  
Allyl Halides

<div><div><div><p>Highly enantioselective Hiyama cross-coupling reactions have been achieved through rhodium(I)-catalyzed dynamic kinetic asymmetric transformations between aryl siloxanes and racemic allyl halides. This process affords valuable enantiomerically enriched allyl arenes and is compatible with heterocyclic allyl chloride electrophiles.</p></div></div></div>

Allylic Chloro-Tetrahydropyridines: Kinetic Resolutions and Stereospecific Reactions of Enantiomerically Enriched Allyl Chlorides

2019 ◽  
Author(s):  
Sedef Karabiyikoglu ◽  
Alexandre Brethomé ◽  
Thomas Palacin ◽  
Robert Paton ◽  
Stephen P. Fletcher
Keyword(s):  
Dft Calculations ◽  
Kinetic Resolution ◽  
Allylic Alkylation ◽  
Substitution Reactions ◽  
Asymmetric Allylic Alkylation ◽  
Allyl Halides ◽  
Stereospecific Reactions ◽  
Kinetic Resolutions

We report the kinetic resolution of racemic allyl chlorides via a copper-catalysed asymmetric allylic alkylation. Novel 3-alkyl substituted tetrahydropyridines and enantioenriched 3-chloro-1,2,3,6-tetrahydropyridines are formed in high enantioselectivities. The piperidine-based allyl halides undergo highly enantiospecific substitution reactions with C, N, O and S-based nucleophiles. Experiments with deuterium-labelled chloro-tetrahydropyridine and DFT calculations were used to investigate the mechanistic pathways of the reactions.

scholarly journals Highly Enantioselective Hiyama Cross-Coupling via Rh-Catalyzed Allylic Arylation of Racemic Allyl Chlorides

2018 ◽  
Author(s):  
Jesus Gonzalez ◽  
Philipp Schäfer ◽  
Stephen P. Fletcher
Keyword(s):  
Allyl Chloride ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Asymmetric Transformations ◽  
Cross Coupling Reactions ◽  
Allyl Halides

<div><div><div><p>Highly enantioselective Hiyama cross-coupling reactions have been achieved through rhodium(I)-catalyzed dynamic kinetic asymmetric transformations between aryl siloxanes and racemic allyl halides. This process affords valuable enantiomerically enriched allyl arenes and is compatible with heterocyclic allyl chloride electrophiles.</p></div></div></div>

Synthesis of B-ring-fluorinated (−)-epicatechin gallate derivatives

2020 ◽  
Vol 18 (21) ◽  
pp. 4024-4028
Author(s):  
David D. S. Thieltges ◽  
Kai D. Baumgarten ◽  
Carina S. Michaelis ◽  
Constantin Czekelius
Keyword(s):  
Kinetic Resolution ◽  
Convergent Sequence ◽  
Epicatechin Gallate

Electronically modified, fluorinated catechins and epicatechins are enantioselectively synthesized in a short, convergent sequence via kinetic resolution.

Probing the Parallel Kinetic Resolution of Racemic Oxazolidinones using Quasi-enantiomeric Profens

2006 ◽  
Author(s):  
Jason Eames ◽  
Gregory Coumbarides ◽  
Marco Dingjan ◽  
Tony Flinn ◽  
Northern Northen ◽  
...  
Keyword(s):  
Kinetic Resolution ◽  
Parallel Kinetic Resolution

Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex

2020 ◽  
Author(s):  
José Tiago Menezes Correia ◽  
Gustavo Piva da Silva ◽  
Camila Menezes Kisukuri ◽  
Elias André ◽  
Bruno Pires ◽  
...  
Keyword(s):  
Electron Donor ◽  
Functional Group ◽  
Photoexcited Electron ◽  
One Pot ◽  
Quaternary Centers ◽  
Metal Free ◽  
Acceptor Complex ◽  
Catalyst Free ◽  
Donor Acceptor ◽  
Radical Cascade

A metal- and catalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a SET event involving a photoexcited electron-donor-aceptor complex between NHPI ester and Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. <a>The method provides an operationally simple, robust and step-economical approach to the construction of diversely functionalized dihydroquinolinones bearing quaternary-centers. A sequential one-pot hydroalkylation-isomerization approach is also allowed giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance was observed in both approaches</a>.

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