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Cycloadditions of Oxacyclic Allenes and a Catalytic Asymmetric Entryway to Enantioenriched Cyclic Allenes
Author(s) -
Yamano Michael M.,
Knapp Rachel R.,
Ngamnithiporn Aurapat,
Ramirez Melissa,
Houk Kendall N.,
Stoltz Brian M.,
Garg Neil K.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201900503
Subject(s) - allene , chemistry , cycloaddition , chirality (physics) , enantioselective synthesis , axial chirality , allylic rearrangement , intramolecular force , catalysis , lewis acids and bases , stereochemistry , combinatorial chemistry , organic chemistry , physics , symmetry breaking , chiral symmetry breaking , quantum mechanics , nambu–jona lasinio model
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.