91881-09-3Relevant articles and documents
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.
Carbene-metal hydrides can be much less acidic than phosphine-metal hydrides: Significance in hydrogenations
Zhu, Ye,Fan, Yubo,Burgess, Kevin
supporting information; scheme or table, p. 6249 - 6253 (2010/06/20)
Acidities of iridium hydride intermediates were shown to be critical in some transformations mediated by the chiral analogues of Crabtree's catalyst, 1-3. To do this, several experiments were undertaken to investigate the acidities of hydrogenation mixtures formed using these iridium-oxazoline complexes. DFT calculations indicated that the acidity difference for Ir-H intermediates in these hydrogenations were astounding; iridium hydride from the N-heterocyclic carbene catalyst 1 was calculated to be around seven pK a units less acidic than those from the P-based complexes 2 and 3. Consistent with this, the carbene complex 1 was shown to be more effective for hydrogenations of acid-sensitive substrates. In deuteration experiments, less "abnormal" deuteration was observed, corresponding to fewer complications from acid-mediated alkene isomerization preceding the D 2-addition step. Finally, simple tests with pH indicators provided visual evidence that phosphine-based catalyst precursors give significantly more acidic reaction mixtures than the corresponding N-heterocyclic carbene ones. These observations indicate carbene-for-phosphine (and similar) ligand substitutions may impact the outcome of catalytic reactions by modifying the acidities of the metal hydrides formed.
Iridium catalysts with bicyclic pyridine-phosphinite ligands: Asymmetric hydrogenation of olefins and furan derivatives
Kaiser, Stefan,Smidt, Sebastian P.,Pfaltz, Andreas
, p. 5194 - 5197 (2007/10/03)
(Chemical Equation Presented) Superior bicyclics: Iridium catalysts as 1 derived from pyridine-phosphinite ligands considerably extend the scope of asymmetric hydrogenation. In addition to various unfunctionalized and functionalized olefins, furans, and benzofurans, for which no catalysts were known before, are also hydrogenated with high enantioselectivity (see scheme).