Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 7, Pages 2792-2800Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c11601
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Funding
- National Science Foundation under CAREER award [CHE-1553802]
- National Science Foundation [CHE-1828183, CHE-0922858, CHE-1726291]
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This study successfully achieved the selective production of different internal alkene isomers using a single cation-responsive iridium catalyst, demonstrating exceptional regioselectivity and stereoselectivity under salt-free conditions. The development of new iridium pincer-crown ether catalysts played a key role in achieving cation-controlled selectivity, providing insights for catalyst development strategies based on noncovalent modifications.
The catalytic transposition of double bonds holds promise as an ideal route to alkenes of value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, normally requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst selectively produces 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 noncovalent modifications.
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