Organometallic Chemistry

Selecting Double Bond Positions with a Single Cation- Responsive Iridium Olefin Isomerization Catalyst

Authors

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-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on non-covalent modifications.

Content

Thumbnail image of Camp_SwitchableRegioselectivity_Manuscript_ChemRxiv_Submission.pdf

Supplementary material

Thumbnail image of Camp_SwitchableRegioselectivity_SI_ChemRxiv_Submission.pdf
Camp SwitchableRegioselectivity SI ChemRxiv Submission
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215c5b
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218c6a
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315c5b
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318c6a
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318c6b
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Na118c6a
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218c6b