Palladium‐katalysierte allylische Substitution an viergliedrigen Ringen: Bildung von η¹‐Allylkomplexen und elektrocyclische Ringöffnung

Abstract

Eine Serie von einzigartigen η1‐Allylpalladiumkomplexen viergliedriger cyclischer Verbindungen mit β‐Wasserstoffatomen wurde hergestellt (siehe Struktur; dba=trans,trans‐Dibenzylidenaceton). Ihre außergewöhnliche Struktur, Reaktivität und Affinität für elektrocyclische Ringöffnungen werden beschrieben.

Palladium‐Catalyzed Asymmetric Allylic Alkylations with Toluene Derivatives as Pronucleophiles

“…[6] In contrast, few palladium-catalyzed allylic substitution reactions with “hard” nucleophiles (generally defined as pronucleophiles with p K a > 25) have materialized. [1a] Recent advances in palladium-catalyzed AAA with “hard” nucleophiles have been reported by Morken and co-workers with allylboronates in allyl-allyl coupling reactions [7] (Scheme 1A) and Maulide and co-workers with the use of dialkylzinc nucleophiles [8] (Scheme 1B). …”

One Hundred Years of the Max‐Planck‐Institut für Kohlenforschung

“…Early collaborative work addressed Rh‐catalyzed asymmetric hydrogenation (Reetz),73 Pd‐catalyzed cross‐coupling (Gooßen),74 and alkene polymerization (Fink, Jolly) 75. More recent collaborative projects covered organocatalysis (List),76 gold catalysis (Fürstner),52 palladium catalysis (Maulide),77 platinum catalysis (Alcarazo),78 and cellulose depolymerization (Rinaldi) 79. These and other joint studies confirmed that DFT calculations are capable of providing detailed insight into the mechanism of catalytic reactions, which is complementary to what can be learnt experimentally and is thus essential for a comprehensive understanding of catalysis.…”

Computational Catalysis—Past, Present, and Future

“…As part of a follow-up study, DFT calculations were performed that provide detailed insight into the palladium-catalyzed electrocyclic ring opening of cyclobutene units in large molecules, which proceeds as a conrotatory reaction in an intermediate palladium-cyclobutene complex, with competing isomer interconversion by h 1 -h 3 -h 1 allyl slippage. [77] 3.6. Joint Projects with the Rinaldi and Schüth Groups Cellulose consists of 1,4-b-linked glucose units, which can be converted to biofuel and industrial platform molecules.…”