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Enantioselective Oxidative (4+3) Cycloadditions between Allenamides and Furans through Bifunctional Hydrogen‐Bonding/Ion‐Pairing Interactions
Author(s) -
Villar Laura,
Uria Uxue,
Martínez Jose I.,
Prieto Liher,
Reyes Efraim,
Carrillo Luisa,
Vicario Jose L.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201704804
Subject(s) - enantioselective synthesis , chemistry , cycloaddition , pairing , bifunctional , hydrogen bond , diene , chirality (physics) , combinatorial chemistry , substrate (aquarium) , photochemistry , organic chemistry , catalysis , molecule , physics , superconductivity , chiral symmetry breaking , oceanography , quantum mechanics , geology , nambu–jona lasinio model , quark , natural rubber
BINOL‐based N‐trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative hydrogen‐bonding and ion‐pairing interactions, enabling an efficient chirality transfer that provide the final adducts with high diastereo‐ and enantioselectivities. Remarkably, the reaction shows a wide substrate scope that includes a variety of substituted allenamides and furans.