Catalytic Transfer Functionalization through Shuttle Catalysis

Abstract

In this Perspective, we describe an emerging type of catalysis that enables the catalytic reversible transfer of chemical entities beyond the well-established transfer hydrogenation reactions. Shuttle catalysis facilitates the transfer of small molecules (e.g., CO, HCN) or reactive intermediates between two substrates in an isodesmic process. In many cases, these often safer processes provide unprecedented synthetic flexibility and complement other catalytic bond-forming and bond-breaking reactions

Formation of a Tunneling Product in the Photorearrangement of o‐Nitrobenzaldehyde

“…[3] Theintermediacyof3 could unequivocally be established by means of matrix-isolation infrared spectroscopy [4] as well as by ultrafast transient visible,infrared, and stimulated Raman spectroscopy. [6] We turned our attention to this intriguing reaction within the broader scope of our studies on tunneling control [7] that must be considered as away of understanding and ultimately controlling chemical reactions as av iable alternative to the well-established principle of kinetic vs.t hermodynamic control. [6] We turned our attention to this intriguing reaction within the broader scope of our studies on tunneling control [7] that must be considered as away of understanding and ultimately controlling chemical reactions as av iable alternative to the well-established principle of kinetic vs.t hermodynamic control.…”

Katalytische, isofunktionelle Reaktionen – Erweiterung des Repertoires an Shuttle‐ und Metathesereaktionen

“…Sie umfasst die Übertragung von Wasserstoff von einem Donor-a uf ein Akzeptormolekül, und da sie reversibel ist, kann sie sowohl fürd ie Hydrierung als auch fürd ie Dehydrierung eingesetzt werden. [14,19] Dies erçffnet die Mçglichkeit fürz ahlreiche andere reversible Übertragungsverfahren. Allerdings ist es lohnenswert, die Tr ansferhydrierung im Kontext der Shuttlekatalyse zu betrachten.…”

Catalytic Isofunctional Reactions—Expanding the Repertoire of Shuttle and Metathesis Reactions

“…Notable examples include some sigmatropic reactions,s uch as the Cope rearrangement [12] and dyotropic rearrangements. [13] Among the reactions involving more than one starting material or product, two groups of transformations can be differentiated:s huttle catalysis reactions [14] and metathesis reactions.…”