Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles

Catalytic enantioselective conjugate additions of organometallic reagents to electron-deficient alkenes and asymmetric allylation of carbonyl compounds are important reactions for the construction of new carbon-carbon bonds. However, a method using an allylnickel species to perform catalytic nucleop...

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Main Author: NGUYEN, THI LE NHON
Format: Thesis (University of Nottingham only)
Language:English
Published: 2020
Subjects:
Online Access:https://eprints.nottingham.ac.uk/59765/
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author NGUYEN, THI LE NHON
author_facet NGUYEN, THI LE NHON
author_sort NGUYEN, THI LE NHON
building Nottingham Research Data Repository
collection Online Access
description Catalytic enantioselective conjugate additions of organometallic reagents to electron-deficient alkenes and asymmetric allylation of carbonyl compounds are important reactions for the construction of new carbon-carbon bonds. However, a method using an allylnickel species to perform catalytic nucleophilic allylation enantioselectively remains considerably underdeveloped and only a handful of examples have been described. In this thesis, enantioselective nickel-catalyzed arylative and alkenylative intramolecular allylations of allenyl electrophiles with boronic acids are described. Enantioselective nickel-catalyzed arylative intramolecular 1,4-allylations An asymmetric nickel-catalyzed desymmetrization of allenyl cyclohexa-2,5-dienones by reaction with arylboronic acids is reported. In this study, nucleophilic allylnickel species, formed by nickel-catalyzed arylation of the allene, undergo 1,4-allylation-cyclization reaction to furnish hexahydroindol-5-ones and hexahydrobenzofuran-5-ones with three contiguous stereocenters in high diastereo- and enantioselectivities (87−99% ee). Enantioselective nickel-catalyzed arylative and alkenylative intramolecular 1,2-allylations An asymmetric nickel-catalyzed cascade reaction of allenyl ketones with boronic acids is described. In this project, a nickel-catalyzed arylation and alkenylation of the allene gives allylnickel species, which undergo a 1,2-allylation-cyclization with tethered ketones to furnish 3-hydroxypyrrolidin-2-ones, 3-hydroxypyrrolidines and 4-hydroxypiperidines in high diastereo- and enantioselectivities.
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spelling nottingham-597652025-02-28T14:45:48Z https://eprints.nottingham.ac.uk/59765/ Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles NGUYEN, THI LE NHON Catalytic enantioselective conjugate additions of organometallic reagents to electron-deficient alkenes and asymmetric allylation of carbonyl compounds are important reactions for the construction of new carbon-carbon bonds. However, a method using an allylnickel species to perform catalytic nucleophilic allylation enantioselectively remains considerably underdeveloped and only a handful of examples have been described. In this thesis, enantioselective nickel-catalyzed arylative and alkenylative intramolecular allylations of allenyl electrophiles with boronic acids are described. Enantioselective nickel-catalyzed arylative intramolecular 1,4-allylations An asymmetric nickel-catalyzed desymmetrization of allenyl cyclohexa-2,5-dienones by reaction with arylboronic acids is reported. In this study, nucleophilic allylnickel species, formed by nickel-catalyzed arylation of the allene, undergo 1,4-allylation-cyclization reaction to furnish hexahydroindol-5-ones and hexahydrobenzofuran-5-ones with three contiguous stereocenters in high diastereo- and enantioselectivities (87−99% ee). Enantioselective nickel-catalyzed arylative and alkenylative intramolecular 1,2-allylations An asymmetric nickel-catalyzed cascade reaction of allenyl ketones with boronic acids is described. In this project, a nickel-catalyzed arylation and alkenylation of the allene gives allylnickel species, which undergo a 1,2-allylation-cyclization with tethered ketones to furnish 3-hydroxypyrrolidin-2-ones, 3-hydroxypyrrolidines and 4-hydroxypiperidines in high diastereo- and enantioselectivities. 2020-07-15 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/59765/1/TLN_Nguyen_Corrected%20Thesis.pdf NGUYEN, THI LE NHON (2020) Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles. PhD thesis, University of Nottingham. Asymmetric catalysis Allylation Arylation Cyclization Nickel
spellingShingle Asymmetric catalysis
Allylation
Arylation
Cyclization
Nickel
NGUYEN, THI LE NHON
Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title_full Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title_fullStr Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title_full_unstemmed Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title_short Enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
title_sort enantioselective nickel-catalyzed arylative intramolecular allylations of allenyl electrophiles
topic Asymmetric catalysis
Allylation
Arylation
Cyclization
Nickel
url https://eprints.nottingham.ac.uk/59765/