Enantioselective Pd-catalyzed allylic amination with self-assembling and non-assembling monodentate phosphine ligands

Organic Carbonates as Alternative Solvents for Palladium‐Catalyzed Substitution Reactions

“…We recently reported already the utility of these ligands in the AAA. [25,29] Results with the Me-phospholane ligand 16 are similar in CH 2 Cl 2 and PC. In both solvents, good or excellent yields accompanied by good ee values were obtained (Table 2, entries 1 and 2).…”

“…[ 25] It seems that the bulky phenyl group prevents the achievement of higher ee values. In toluene and dichloromethane, the reactivity of the catalyst was low ( Table 2, entries 8 and 10).…”

“…[25] We collected several pieces of evidence that the formation of the desired hydrogen-bonding-based assemblies is strongly affected by the choice of the solvent. [24,25] Moreover, we investigated the effect of such ligands in Rh-catalyzed hydrogenations in fluorinated alcohols. [26] Results and Discussion…”

Determination of the Conformation of the Key Intermediate in an Enantioselective Palladium‐Catalyzed Allylic Substitution from Residual Dipolar Couplings

“…[3,4] Extensive studies have been devoted to probing the origin of stereoselection in allylic substitutions with bidentate ligands, of which only few can be mentioned here. [5][6][7][8][9][10][11][12][13][14] For systems with monodentate ligands, [15][16][17][18][19][20][21] as is the case in the present study (see 1), several X-ray structures of catalyst-substrate complexes exist, but to our knowledge no detailed NMR spectroscopic study in solution has yet been performed. The conformation of an intermediate complex in solution might not necessarily resemble that determined crystallographically.…”

Bestimmung der Konformation des Schlüsselintermediats einer enantioselektiven Palladium‐katalysierten allylischen Substitution mithilfe dipolarer Restkopplungen

“…[5][6][7][8][9][10][11][12][13][14] Für Systeme mit einzähnigen Liganden, wie dem hier untersuchten (1), existieren einige Röntgenkristallstrukturen entsprechender Katalysator-Substrat-Komplexe. [15][16][17][18][19][20][21] [22][23][24][25][26][27][28][29][30] und seit kurzem auch in organischen Molekülen in räumliche Beziehung zueinander zu setzen. [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46] Der hier mithilfe von RDCs untersuchte Komplex wurde von Helmchen et al als ein selbstorganisiertes PalladiumKatalysatorsystem beschrieben.…”