Influence of Achiral Phosphine Ligands on a Synergistic Organo‐ and Palladium‐Catalyzed Asymmetric Allylic Alkylation
Abstract: An unusual diastereodivergent stereoselective allylation reaction is presented. It consists of a palladium‐catalyzed allylation reaction of an organocatalytically generated amino isobenzofulvene, where the diastereoselectivity is controlled by the electronic properties of a monodentate, achiral ligand on palladium. One major diastereoisomer is formed using triarylphosphines substituted with neutral or electron‐donating substituents of the aryl group, while those with electron‐withdrawing substituents favor the other diastereoisomer. The diastereoselectivity correlates with the Taft inductive parameter of substituents on the triarylphosphine ligand on palladium. The synergistic reaction involves both a catalytic secondary amine catalyst for the indene‐aldehyde activation and the monodentate phosphine ligands on palladium, affording a highly enantioselective reaction with up to 98 % enantiomeric excess. Based on computational investigations, the role of the monodentate phosphine ligand on the diastereoselectivity is discussed.
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Bibliographic citation
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Influence of Achiral Phosphine Ligands on a Synergistic Organo‐ and Palladium‐Catalyzed Asymmetric Allylic Alkylation ; day:27 ; month:10 ; year:2022 ; extent:1
Chemistry - a European journal ; (27.10.2022) (gesamt 1)
- Creator
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McLeod, David
Inunnguaq Jessen, Nicolaj
Nguyen, Thanh V. Q.
Espe, Marcus
Erickson, Jeremy David
Anker Jørgensen, Karl
Yang, Limin
Houk, Kendall N.
- DOI
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10.1002/chem.202202951
- URN
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urn:nbn:de:101:1-2022102715413788013330
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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15.08.0016, 6:35 AM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- McLeod, David
- Inunnguaq Jessen, Nicolaj
- Nguyen, Thanh V. Q.
- Espe, Marcus
- Erickson, Jeremy David
- Anker Jørgensen, Karl
- Yang, Limin
- Houk, Kendall N.
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The Enantioselective Tsuji Decarboxylative Allylic Alkylation
The Allylic Alkylation of Ketone Enolates
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Allylic C(sp 3 )-H alkylation via synergistic organo- and photoredox catalyzed radical addition to imines
Asymmetric α-C(sp 3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis
Asymmetric Decarboxylative Allylic Alkylation of Acyclic Enol Carbonates
Copper-Catalyzed Asymmetric Allylic Alkylation with Organolithium Reagents
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Pd-Catalyzed Allylic Alkylation of Ketones
The Enantioselective Tsuji Decarboxylative Allylic Alkylation
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Catalytic Asymmetric Allylic Alkylation with Vinylaluminum Reagents
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