Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/89326
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dc.contributor.authorCao, Weidien
dc.contributor.authorTan, Davinen
dc.contributor.authorLee, Richmonden
dc.contributor.authorTan, Choon-Hongen
dc.date.accessioned2018-05-22T09:23:03Zen
dc.date.accessioned2019-12-06T17:22:57Z-
dc.date.available2018-05-22T09:23:03Zen
dc.date.available2019-12-06T17:22:57Z-
dc.date.issued2018en
dc.identifier.citationCao, W., Tan, D., Lee, R., & Tan, C.-H. (2018). Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair. Journal of the American Chemical Society, 140(5), 1952-1955.en
dc.identifier.issn0002-7863en
dc.identifier.urihttps://hdl.handle.net/10356/89326-
dc.description.abstractHighly enantioselective bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary alcohols in high yields with excellent enantioselectivities (up to 95% ee). The isolation of an α-silylcarbinol intermediate as well as DFT calculations revealed that the 1,2-anionotropic rearrangement occurred via a bisguanidinium silicate ion pair, which is the stereodetermining step. The chiral center formed is then retained without inversion through the subsequent [1,2]-Brook rearrangement. Crotyl acylsilanes were smoothly transformed into homoallylic linear crotyl alcohols with retention of E/Z geometry, and no branched alcohols were detected. This clearly suggested that the 1,2-anionotropic rearrangement occurred through a three-membered instead of a five-membered transition state.en
dc.format.extent5 p.en
dc.language.isoenen
dc.relation.ispartofseriesJournal of the American Chemical Societyen
dc.rights© 2018 American Chemical Society. This is the author created version of a work that has been peer reviewed and accepted for publication by Journal of the American Chemical Society, American Chemical Society. It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1021/jacs.7b13056].en
dc.subjectEnantioselectiveen
dc.subjectBisguanidinium Silicate Ionen
dc.titleEnantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pairen
dc.typeJournal Articleen
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen
dc.identifier.doi10.1021/jacs.7b13056en
dc.description.versionAccepted versionen
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