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.
- Standort
-
Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
-
Online-Ressource
- Sprache
-
Englisch
- Erschienen in
-
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)
- Urheber
-
McLeod, David
Inunnguaq Jessen, Nicolaj
Nguyen, Thanh V. Q.
Espe, Marcus
Erickson, Jeremy David
Anker Jørgensen, Karl
Yang, Limin
Houk, Kendall N.
- DOI
-
10.1002/chem.202202951
- URN
-
urn:nbn:de:101:1-2022102715413788013330
- Rechteinformation
-
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
-
15.08.2025, 07:35 MESZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- McLeod, David
- Inunnguaq Jessen, Nicolaj
- Nguyen, Thanh V. Q.
- Espe, Marcus
- Erickson, Jeremy David
- Anker Jørgensen, Karl
- Yang, Limin
- Houk, Kendall N.
Ähnliche Objekte (12)
Palladium-Catalyzed Asymmetric Allylic Alkylation Reaction of 2-Monosubstituted Indolin-3-ones
Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters
Enantioselective Palladium-Catalyzed Allylic Dearomatization
Pd-Catalyzed Allylic Alkylation of Ketones
The Allylic Alkylation of Ketone Enolates
The Enantioselective Tsuji Decarboxylative Allylic Alkylation
Catalytic Asymmetric Allylic Alkylation with Vinylaluminum Reagents
Palladium-Catalyzed Asymmetric Synthesis of Phosphine Sulfonates
Asymmetric α-C(sp 3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis
Allylic C(sp 3 )-H alkylation via synergistic organo- and photoredox catalyzed radical addition to imines
Asymmetric Decarboxylative Allylic Alkylation of Acyclic Enol Carbonates
Copper-Catalyzed Asymmetric Allylic Alkylation with Organolithium Reagents
Palladium-Catalyzed Asymmetric Allylic Alkylation Reaction of 2-Monosubstituted Indolin-3-ones
Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters
Enantioselective Palladium-Catalyzed Allylic Dearomatization
Pd-Catalyzed Allylic Alkylation of Ketones
The Allylic Alkylation of Ketone Enolates
The Enantioselective Tsuji Decarboxylative Allylic Alkylation
Catalytic Asymmetric Allylic Alkylation with Vinylaluminum Reagents
Palladium-Catalyzed Asymmetric Synthesis of Phosphine Sulfonates
Asymmetric α-C(sp 3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis
Allylic C(sp 3 )-H alkylation via synergistic organo- and photoredox catalyzed radical addition to imines
Asymmetric Decarboxylative Allylic Alkylation of Acyclic Enol Carbonates
Copper-Catalyzed Asymmetric Allylic Alkylation with Organolithium Reagents
Palladium-Catalyzed Asymmetric Allylic Alkylation Reaction of 2-Monosubstituted Indolin-3-ones
Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters
Enantioselective Palladium-Catalyzed Allylic Dearomatization
Pd-Catalyzed Allylic Alkylation of Ketones
The Allylic Alkylation of Ketone Enolates
The Enantioselective Tsuji Decarboxylative Allylic Alkylation
Catalytic Asymmetric Allylic Alkylation with Vinylaluminum Reagents
Palladium-Catalyzed Asymmetric Synthesis of Phosphine Sulfonates
Asymmetric α-C(sp 3)−H allylic alkylation of primary alkylamines by synergistic Ir/ketone catalysis
Allylic C(sp 3 )-H alkylation via synergistic organo- and photoredox catalyzed radical addition to imines
Asymmetric Decarboxylative Allylic Alkylation of Acyclic Enol Carbonates