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Radical Reactions of 1,4-Alkadiynes: Metal Coordination as an Effective Tool for Controlling the Regio- and Stereoselectivity of the C–C Bond Formation
journal contribution
posted on 2015-09-14, 00:00 authored by Gagik G. Melikyan, Bryan AnkerA novel method for selective generation
of radicals in 1,4-alkadiynes
is developed by employing a π-bonded Co2(CO)6 core as a triple-bond immobilizing, cation-stabilizing, and
radical-guiding auxiliary group. The isolation of α-alkynyl-cobalt-complexed
propargyl cations and their reduction with zinc occurred in a regio-
and stereoselective manner, giving rise to tetraethynylethanes with
predominant formation of d,l-diastereomers (82–93%).
The methodology provides an easy access to tetraethynylethanes and,
upon oxidation, to practically important tetraethynylethenes. We also
report on the novel phenomenon of “chiralization by metal complexation”,
with achiral tetraynes being converted to chiral bis-clusters due
to highly regio- and stereoselective complexation of the acetylenic
groups.
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Keywords
coregenerationradicaltetraethynylethenecationAlkadiynenovel phenomenonacetylenic groupsstereoselective complexationmethodologyaccesstetraethynylethaneRegioControllingStereoselectivityalkadiyneimmobilizingpropargylFormationAmethodachiral tetraynesEffective Tooloxidationstereoselective mannerMetal CoordinationRadical ReactionsBondregioisolationchiralizationformation