Tertiary Arsine Ligands for Pd-Catalyzed Direct Arylation

Catalysts for direct arylations have been extensively studied for the efficient synthesis of (hetero)­biaryl compounds. Phosphine ligands are pivotal in this field, and electron-deficient phosphine ligands are advantageous for direct arylation. Due to its relatively weak σ-donation ability, arsenic...

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Bibliographic Details
Published inOrganometallics Vol. 43; no. 3; pp. 322 - 329
Main Authors Ogawa, Kenta, Sumida, Akifumi, Yumura, Takashi, Imoto, Hiroaki, Naka, Kensuke
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 12.02.2024
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
PALLADIUM
PHOSPHINE
TRIPHENYLARSINE
BOND FUNCTIONALIZATIONS
CHEMISTRY
METALATION-DEPROTONATION MECHANISM
SIMPLE ARENES
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Summary:Catalysts for direct arylations have been extensively studied for the efficient synthesis of (hetero)­biaryl compounds. Phosphine ligands are pivotal in this field, and electron-deficient phosphine ligands are advantageous for direct arylation. Due to its relatively weak σ-donation ability, arsenic is considered an ideal candidate for designing electron-deficient ligands. However, no studies have explored the relationship between the structure of the arsine ligands and their catalytic activity for direct arylation. In this study, we synthesized 27 arsine ligands with varying electron-donating and steric properties. Tris­(o-trifluorotolyl)­arsine, an electron-deficient and bulky ligand, exhibited the highest efficiency in a model reaction between 2-propylthiophene and 4-bromobenzotrifluoride. Both experimental and computational studies revealed the mechanism of direct arylation using arsine ligands. This is the first comprehensive investigation of an arsine-ligated catalytic direct arylation.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.3c00464