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Published April 16, 2019 | Supplemental Material + Accepted Version
Journal Article Open

Cycloadditions of Oxacyclic Allenes and a Catalytic Asymmetric Entryway to Enantioenriched Cyclic Allenes


The chemistry of strained cyclic alkynes has undergone a renaissance over the past two decades. However, a related species, strained cyclic allenes, especially heterocyclic derivatives, have only recently resurfaced and represent another class of valuable intermediates. We report a mild and facile means to generate the parent 3,4‐oxacyclic allene from a readily accessible silyl triflate precursor, and then trap it in (4+2), (3+2), and (2+2) reactions to provide a variety of cycloadducts. In addition, we describe a catalytic, decarboxylative asymmetric allylic alkylation performed on an α‐silylated substrate, to ultimately permit access to an enantioenriched allene. Generation and trapping of the enantioenriched cyclic allene occurs with complete transfer of stereochemical information in a Diels–Alder cycloaddition through a point‐chirality, axial‐chirality, point‐chirality transfer process.

Additional Information

© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Accepted manuscript online: 27 February 2019; Manuscript accepted: 25 February 2019; Manuscript revised: 24 February 2019; Manuscript received: 21 January 2019. The authors are grateful to NIH‐NIGMS (R01 GM123299‐01A1 and R01 GM117016 to N.K.G. and R01GM080269 to B.M.S), Caltech, the Trueblood Family (to N.K.G.) and UCLA for support. M.M.Y. acknowledges the National Science Foundation GRFP (DGE‐1144087) and the Foote Family. A.N. thanks the Royal Thai Government Scholarship Program. Dr. Scott Virgil (Caltech) is thanked for instrumentation and SFC assistance. These studies were supported by shared instrumentation grants from the NSF (CHE‐1048804) and the National Center for Research Resources (S10RR025631). This study used computational and storage services associated with the Hoffman2 Shared Cluster provided by UCLA Institute for Digital Research and Education's Research Technology Group. The authors declare no conflict of interest.

Attached Files

Accepted Version - nihms-1019240.pdf

Supplemental Material - anie201900503-s1-garg-anie201900503-si.pdf


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