767-60-2Relevant articles and documents
Cyclopropenylgold(I) Complexes as Aurated Carbenoids or Quasi-Carbenes
Mulks, Florian F.,Antoni, Patrick W.,Rominger, Frank,Hashmi, A. Stephen K.
, p. 1810 - 1821 (2018/03/21)
Highly strained hydrocarbons have always been a research target of high interest. Due to their untypical electronic structure, they show interesting reactivity patterns and can easily be activated by π-coordination to or insertion reactions with metal complexes. Herein we report the synthesis of a range of 3,3-disubstituted cyclopropenylgold(I) complexes. The synthesis of such compounds with a metal, which usually easily activate cyclopropenes is a double-edged sword. We found σ-bound vinylic gold to generally have a strong stabilizing effect in terms of ring strain. The complexes show a strong distortion, preactivating the cyclopropenyls towards the ring-opening mode which thermally generates 1-aurated vinylcarbenes which is reflected by a much faster conversion (Ea of 10 kcal/mol instead of 40 kcal/mol, the reaction proceeds at temperatures as low as ?20 °C instead of 200 °C reported in the literature). In 3-phenyl-cyclopropenyl complexes, these could be trapped intramolecularly to give indenylgold(I) complexes. The properties of these highly strained complexes were investigated, utilizing a range of analytical and experimental procedures and Kohn-Sham density functional theoretic methods. (Figure presented.).
Endo-selective pd-catalyzed silyl methyl heck reaction
Parasram, Marvin,Iaroshenko, Viktor O.,Gevorgyan, Vladimir
supporting information, p. 17926 - 17929 (2015/03/04)
A palladium (Pd)-catalyzed endo-selective Heck reaction of iodomethylsilyl ethers of phenols and aliphatic alkenols has been developed. Mechanistic studies reveal that this silyl methyl Heck reaction operates via a hybrid Pd-radical process and that the silicon atom is crucial for the observed endo selectivity. The obtained allylic silyloxycycles were further oxidized into (Z)-alkenyldiols.
Enantiopure C1-symmetric bis(imino)pyridine cobalt complexes for asymmetric alkene hydrogenation
Monfette, Sebastien,Turner, Zoe R.,Semproni, Scott P.,Chirik, Paul J.
, p. 4561 - 4564 (2012/04/23)
Enantiopure C1-symmetric bis(imino)pyridine cobalt chloride, methyl, hydride, and cyclometalated complexes have been synthesized and characterized. These complexes are active as catalysts for the enantioselective hydrogenation of geminal-disubstituted olefins.
