1324010-90-3Relevant academic research and scientific papers
Copper(I)-catalyzed regio- and chemoselective single and double addition of nucleophilic silicon to propargylic chlorides and phosphates
Hazra, Chinmoy K.,Oestreich, Martin
supporting information; experimental part, p. 4010 - 4013 (2012/10/08)
Copper(I)-catalyzed propargylic substitution of linear precursors with (Me2PhSi)2Zn predominantly yields the γ isomer independent of the propargylic leaving group. The thus formed allenylic silane reacts regioselectively with another equivalent of (Me2PhSi) 2Zn, yielding a bifunctional building block with allylic and vinylic silicon groups. The reaction rates of both steps are well-balanced for chloride (γ:α ≥ 99:1) where the propargylic displacement occurs quantitatively prior to the addition step. Substitutions of α-branched propargylic phosphates are also reported.
Copper(I)-catalyzed regioselective propargylic substitution involving Si-B bond activation
Vyas, Devendra J.,Hazra, Chinmoy K.,Oestreich, Martin
, p. 4462 - 4465 (2011/10/08)
The silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation allows several γ-selective propargylic substitutions. The regioselectivity (γ:α ratio) is strongly dependent on the propargylic leaving group. Chloride is superior to oxygen leaving groups in linear substrates (γ:α > 99:1), and it is only the phosphate group that also shows promising regiocontrol (γ:α = 90:10). That leaving group produces superb γ-selectivity (γ:α > 99:1) in α-branched propargylic systems, and enantioenriched substrates react with excellent central-to-axial chirality transfer.
