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

Yamano, Michael M. and Knapp, Rachel R. and Ngamnithiporn, Aurapat and Ramirez, Melissa and Houk, Kendall N. and Stoltz, Brian M. and Garg, Neil K. (2019) Cycloadditions of Oxacyclic Allenes and a Catalytic Asymmetric Entryway to Enantioenriched Cyclic Allenes. Angewandte Chemie International Edition, 58 (17). pp. 5653-5657. ISSN 1433-7851. PMCID PMC6456397. doi:10.1002/anie.201900503.

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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.

Item Type:Article
Related URLs:
URLURL TypeDescription CentralArticle
Knapp, Rachel R.0000-0003-1792-3090
Ngamnithiporn, Aurapat0000-0002-5389-8171
Ramirez, Melissa0000-0002-4038-2029
Houk, Kendall N.0000-0002-8387-5261
Stoltz, Brian M.0000-0001-9837-1528
Garg, Neil K.0000-0002-7793-2629
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.
Funding AgencyGrant Number
NIHR01 GM123299-01A1
NIHR01 GM117016
NIHR01 GM080269
NSF Graduate Research FellowshipDGE-1144087
Royal Thai Government Scholarship ProgramUNSPECIFIED
Subject Keywords:Cyclic allenes; Cycloadditions; enantioselective; Heterocycles; catalysis
Issue or Number:17
PubMed Central ID:PMC6456397
Record Number:CaltechAUTHORS:20190227-131909461
Persistent URL:
Official Citation:M. M. Yamano, R. R. Knapp, A. Ngamnithiporn, M. Ramirez, K. N. Houk, B. M. Stoltz, N. K. Garg, Angew. Chem. Int. Ed. 2019, 58, 5653; doi: 10.1002/anie.201900503
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:93305
Deposited By: Tony Diaz
Deposited On:27 Feb 2019 21:32
Last Modified:01 Mar 2022 21:13

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