Carlson Paul R, Burns Alexander S, Shimizu Emily A, Wang Shilin, Rychnovsky Scott D
Department of Chemistry, University of California at Irvine, 1102 Natural Sciences II, Irvine, California 92697, United States.
Org Lett. 2021 Mar 19;23(6):2183-2188. doi: 10.1021/acs.orglett.1c00340. Epub 2021 Feb 26.
The utility of the dioxasiline ring as a π-facial directing group in the intramolecular Diels-Alder cyclization is explored. An initial investigation of substrate scope demonstrates that the rigidity of this directing group delivers robust stereocontrol across a number of substrates, affording single diastereomers in moderate to good yields. A mechanistic investigation reveals that the reactive diene is formed through γ deprotonation followed by [1,5] hydride shifts.
探索了二氧杂硅环作为分子内狄尔斯-阿尔德环化反应中π-面导向基团的效用。对底物范围的初步研究表明，该导向基团的刚性在多种底物上提供了强大的立体控制，以中等至良好的产率得到单一非对映异构体。机理研究表明，反应性二烯是通过γ去质子化，然后进行[1,5]氢迁移形成的。
