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

Angewandte Chemie
Michael M YamanoNeil K Garg

Abstract

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.

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Citations

Jul 23, 2020·Chemical Communications : Chem Comm·Liang WeiChun-Jiang Wang
Aug 28, 2020·Nature·Michael M YamanoNeil K Garg
Jun 8, 2021·Chemical Science·Srinivas ThadkapallyChristopher J T Hyland
Jun 19, 2021·Journal of the American Chemical Society·Andrew V KelleghanNeil K Garg
Apr 15, 2021·Angewandte Chemie·Melissa RamirezKendall N Houk
Aug 3, 2021·JACS Au·Sarah M AnthonyNeil K Garg
Mar 7, 2019·The Journal of Organic Chemistry·Jason V ChariNeil K Garg
May 22, 2020·Organic Letters·Matthew S McVeighNeil K Garg
Apr 9, 2020·Journal of the American Chemical Society·Matthias V WestphalStuart L Schreiber
Jul 24, 2020·The Journal of Organic Chemistry·Moustapha FortunatoFlorian Jaroschik

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