posted on 2019-01-14, 00:00authored bySaswata Gupta, Peipei Xie, Yuanzhi Xia, Daesung Lee
The selectivity between two different manifolds of reactions of arynes reacting with functionalized alkenes is described. Arynes generated from bis-1,3-diynes react with various trisubstituted and 1,1-disubstituted alkenes including methallyl amine, prenyl azide, and methacrylic acid, providing mainly addition products of the polar heteroatom functionalities over the Alder-ene products of the alkene segment. The selectivity, however, intricately depends on the substituent pattern of the alkene. Except for the most reactive 2-propenyl group-containing aldehyde, α,β-unsaturated aldehydes generally participated in an addition reaction, generating chromene derivatives.
Funding
Financial Support from NSF (1361620, DL), Tacoma Technology, and NSFC (2137278 and 21572163, YX) and the mass spectrometry facility at UIUC is greatly acknowledged.
History
Publisher Statement
Copyright @ Royal Society of Chemistry
Citation
Gupta, S., Xie, P., Xia, Y., & Lee, D. (2018). Reactivity of arynes toward functionalized alkenes: Intermolecular Alder-ene: Vs. addition reactions. Organic Chemistry Frontiers, 5(14), 2208-2213. doi:10.1039/c8qo00470f