ArticleJournal of the American Chemical Society2015
Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution.
Article in Journal of the American Chemical Society, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 15 papers.
What it found
Each row is one number read from the abstract, on the scale the paper reported it, with its interval. Left of the dashed line favours the treatment, right favours the comparator. Under each row is the sentence it came from. New to these charts? A ten-minute tutorial.
The abstract states no effect estimate the extractor could read, or names no intervention and outcome on the map, so this paper lights no cell and moves no belief. It is still indexed, cited and linked below.
The trial behind it
Trials whose registry record cites this paper, or whose number appears in the abstract. A trial that started after this paper was published is citing it as background, not reporting it.
Neither the registry nor the abstract names a trial number. If this is a trial report, that itself is worth knowing.
Who cites it
15 citing papers in PubMed, 82 citations in OpenAlex.
- Article
- Iridium-Catalyzed Regio- and Enantioselective Reverse Prenylation of Tryptamines and Other 3-Substituted Indoles.Journal of the American Chemical Society · 2025Article
- Computational Study of the Ir-Catalyzed Formation of Allyl Carbamates from COOrganometallics · 2024Article
- Asymmetric α-C(spNature communications · 2024Article
- Chiral Amines via Enantioselective π-Allyliridium-Accounts of chemical research · 2022Article
- Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malonates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers.Journal of the American Chemical Society · 2022Article
- Chirality memory of α-methylene-π-allyl iridium species.Chemical science · 2021Article
- Enantioselective Iridium-Catalyzed Allylation of Nitroalkanes: Entry to β-Stereogenic α-Quaternary Primary Amines.Journal of the American Chemical Society · 2021Article
- Mechanistic insights into rhodium-catalyzed enantioselective allylic alkylation for quaternary stereogenic centers.Chemical science · 2020Article
- Intermolecular Stereoselective Iridium-Catalyzed Allylic Alkylation: An Evolutionary Account.Synlett : accounts and rapid communications in synthetic organic chemistry · 2018Article
- Stereodivergent Allylation of Azaaryl Acetamides and Acetates by Synergistic Iridium and Copper Catalysis.Journal of the American Chemical Society · 2018Article
- Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation.Angewandte Chemie (International ed. in English) · 2017Article
- Iridium-Catalyzed Enantioselective Allylic Substitution of Aliphatic Esters with Silyl Ketene Acetals as the Ester Enolates.Angewandte Chemie (International ed. in English) · 2017Article
- Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.Journal of the American Chemical Society · 2017Article
- Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Trisubstituted Allylic Electrophiles.Angewandte Chemie (International ed. in English) · 2016Article
Corrections and comments
PubMed lists nothing against this paper. Absence here is not a guarantee, only a check that was made.
Authors and funding
4 authors at 2 institutions in 1 country.
Funding
Abstract
Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl]2 and P(OPh)3 by cyclometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C-H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.
Indexed as
Identifiers
What OpenQuestion holds
Registered trials
Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.