Rhenium-Promoted C-C Bond-Cleavage Reactions of Internal Propargyl Alcohols.
Kui Fun LeeWei BaiHerman H Y SungIan D WilliamsZhenyang LinGuochen JiaPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2018)
The first examples of C-C bond cleavage reactions of internal propargyl alcohols to give vinylidene complexes are described. Treatment of [Re(dppm)3 ]I with RC≡CC(OH)R'R'' (R=aryl, alkyl; C(OH)R'R''=C(OH)Ph2, C(OH)Me2 , C(OH)HPh, C(OH)H2 ) produced the vinylidene complexes ReI(=C=CHR)(dppm)2 with the elimination of C(O)R'R''. Computational studies support that the reactions proceed through a β-alkynyl elimination of alkoxide intermediates Re{OC(R')(R'')C≡CR}(dppm)2 .