2021
DOI: 10.1021/jacs.0c11601
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Selecting Double Bond Positions with a Single Cation-Responsive Iridium Olefin Isomerization Catalyst

Abstract: The catalytic transposition of double bonds holds promise as an ideal route to alkenes with value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst is developed for the selective production of either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-buten… Show more

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Cited by 47 publications
(33 citation statements)
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“…Pincer ligands and metal–ligand cooperativity (MLC) represent two of the most active themes in the development of transition metal and main group metal chemistry and catalysis, and there has been a substantial overlap between these areas of investigation. Numerous examples of pincer ligands engaging in novel catalytic and stoichiometric MLC-related reactions have been and continue to be reported. Yet, despite the large number of pincer ligands for which MLC is based on a coordinating N atom, there are very few examples involving the next congener, phosphorus. In particular, in spite of the great value that has been proven for addition of H 2 across M–N bonds, there are relatively few examples of H 2 addition across a phosphorus metal bond and even fewer examples of the reverse elimination of H 2 . , …”
Section: Introductionmentioning
confidence: 99%
“…Pincer ligands and metal–ligand cooperativity (MLC) represent two of the most active themes in the development of transition metal and main group metal chemistry and catalysis, and there has been a substantial overlap between these areas of investigation. Numerous examples of pincer ligands engaging in novel catalytic and stoichiometric MLC-related reactions have been and continue to be reported. Yet, despite the large number of pincer ligands for which MLC is based on a coordinating N atom, there are very few examples involving the next congener, phosphorus. In particular, in spite of the great value that has been proven for addition of H 2 across M–N bonds, there are relatively few examples of H 2 addition across a phosphorus metal bond and even fewer examples of the reverse elimination of H 2 . , …”
Section: Introductionmentioning
confidence: 99%
“…As mentioned above, our Ru-1 complex is also a highly efficient catalyst for the isomerization of CC double bonds. Thus, when 4-phenyl-1-butene 1-2t was employed as the substrate under the alkene isomerization conditions, in the absence of H 2 gas (eq ), 3-2t was obtained selectively after 48 h, following the CC bond shift to the 3-position (92% yield, >20:1 for 3-2t/2-2t ) . Interestingly, NACET was found to be too poisonous to allow for efficient isomerization in this case, but the addition of a catalytic amount of HexNH 2 to Ru-1 enabled it to selectively catalyze the isomerization of the CC bond to the 2-position, affording product 2-2t in 89% yield (>20:1 for 2-2t/3-2t ). …”
Section: Resultsmentioning
confidence: 95%
“…Monitoring the catalysis at short reaction times (15 min) and assuming zero-order reaction kinetics led to an estimated TOF of 2004 h –1 with a t 1/2 = 0.016 h. These results are only estimates because the amount of isomerized products was greater than 10% where zero-order kinetics can no longer be assumed. However, these results seem to align well with similarly reported isomerization catalysts …”
Section: Results and Discussionmentioning
confidence: 97%