1301680-12-5Relevant articles and documents
Selecting double bond positions with a single cation-responsive iridium olefin isomerization catalyst
Camp, Andrew M.,Kita, Matthew R.,Blackburn, P. Thomas,Dodge, Henry M.,Chen, Chun-Hsing,Miller, Alexander J.M.
, p. 2792 - 2800 (2021/03/01)
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.
