Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation

David McLeod; Nicolaj Inunnguaq Jessen; Thanh V.Q. Nguyen; Marcus Espe; Jeremy David Erickson; Karl Anker Jørgensen; Limin Yang; K. N. Houk

doi:10.1002/chem.202202951

Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation

David McLeod, Nicolaj Inunnguaq Jessen, Thanh V.Q. Nguyen, Marcus Espe, Jeremy David Erickson, Karl Anker Jørgensen^*, Limin Yang, K. N. Houk

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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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.

Original language	English
Article number	e202202951
Journal	Chemistry - A European Journal
Volume	28
Issue	71
ISSN	0947-6539
DOIs	https://doi.org/10.1002/chem.202202951
Publication status	Published - Dec 2022

Keywords

allylic alkylation
asymmetric synthesis
DFT calculations
mechanism
synergistic catalysis

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10.1002/chem.202202951Licence: CC BY

Chemistry A European J - 2022 - McLeodFinal published version, 3.86 MBLicence: CC BY

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@article{99f582f81e42439e81e00c4ea837515b,

title = "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.",

keywords = "allylic alkylation, asymmetric synthesis, DFT calculations, mechanism, synergistic catalysis",

author = "David McLeod and {Inunnguaq Jessen}, Nicolaj and Nguyen, {Thanh V.Q.} and Marcus Espe and Erickson, {Jeremy David} and {Anker J{\o}rgensen}, Karl and Limin Yang and Houk, {K. N.}",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.",

year = "2022",

month = dec,

doi = "10.1002/chem.202202951",

language = "English",

volume = "28",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

number = "71",

}

Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation. / McLeod, David; Inunnguaq Jessen, Nicolaj; Nguyen, Thanh V.Q. et al.
In: Chemistry - A European Journal, Vol. 28, No. 71, e202202951, 12.2022.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

TY - JOUR

T1 - Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation

AU - McLeod, David

AU - Inunnguaq Jessen, Nicolaj

AU - Nguyen, Thanh V.Q.

AU - Espe, Marcus

AU - Erickson, Jeremy David

AU - Anker Jørgensen, Karl

AU - Yang, Limin

AU - Houk, K. N.

PY - 2022/12

Y1 - 2022/12

N2 - 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.

AB - 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.

KW - allylic alkylation

KW - asymmetric synthesis

KW - DFT calculations

KW - mechanism

KW - synergistic catalysis

U2 - 10.1002/chem.202202951

DO - 10.1002/chem.202202951

M3 - Journal article

C2 - 36129762

AN - SCOPUS:85141144536

SN - 0947-6539

VL - 28

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 71

M1 - e202202951

ER -

Influence of Achiral Phosphine Ligands on a Synergistic Organo- and Palladium-Catalyzed Asymmetric Allylic Alkylation

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