Güneş, YakupPolat, Muhammed FatihŞahin, ErtanFleming, Fraser F.Altundaş, Ramazan2019-12-232019-12-232010Güneş, Y., Polat, M. F., Sahin, E., Fleming, F. F., & Altundas, R. (2010). Enantioselective synthesis of cyclic, quaternary oxonitriles. The Journal of organic chemistry, 75(21), 7092-7098.https://pubs.acs.org/doi/10.1021/jo1011202https://hdl.handle.net/20.500.12604/2347Quaternary oxonitriles are stereoselectively generated from the union of five-, six-, and seven-membered 2-chloroalkenecarbonitriles with chiral alcohols via a Claisen rearrangement. The strategy rests on a new conjugate addition-elimination of allylic alkoxides to 2-chlorocycloalkenecarbonitriles to afford substituted 2-alkoxyalkenenitriles. Subsequent thermolysis unmasks a cyclic oxonitrile while selectively forming a new quaternary center with enantiomeric ratios typically greater than 9:1. The overall alkylation strategy addresses the challenge of enantioselectively generating hindered, quaternary centers while simultaneously installing ketone, nitrile, and olefin functionalities.eninfo:eu-repo/semantics/embargoedAccessQuaternary OxonitrilesEnantioselective SynthesisArticle75217092709810.1021/jo1011202