Black‐Swan‐Ereignisse in der organischen Synthese

Abstract

Verbreitet sich ein Forschungsgebiet „wie ein Virus“, geht dies zumeist mit Veränderungen in der Lehrmeinung einher. Oft finden sich dann in der älteren Literatur nachträglich Indizien, dass die konventionelle Vorstellung nicht richtig sein konnte. Diese Antezedentien werden als „Black‐Swan“‐Ereignisse bezeichnet. Das Bild zeigt die virusartige Verbreitung der Forschungen zur homogenen Goldkatalyse.

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

“…The air-and water-stability of gold catalysts, coupled with their ability to promote complex transformations under mild conditions has attracted considerable interest from the academic community. [1] Despite the rapid pace of recent developments, the majority of gold-catalyzed processes rely on a select few reaction manifolds: 1) Lewis acid catalysis, 2) p-activation, and 3) the generation of carbenoid intermediates (Scheme 1 A). [2] While these modes of reactivity have yielded important catalytic methodologies of broad scope and synthetic utility, [3] they are typified by catalytic cycles wherein gold maintains a +1 oxidation state, in stark contrast to the 2electron redox cycles characteristic of late transition metal catalysis.…”

Gold‐Catalyzed Allylation of Aryl Boronic Acids: Accessing Cross‐Coupling Reactivity with Gold

“…The air‐ and water‐stability of gold catalysts, coupled with their ability to promote complex transformations under mild conditions has attracted considerable interest from the academic community 1. Despite the rapid pace of recent developments, the majority of gold‐catalyzed processes rely on a select few reaction manifolds: 1) Lewis acid catalysis, 2) π‐activation, and 3) the generation of carbenoid intermediates (Scheme ) 2.…”

Improvement in the One‐Carbon Chain Extension of Esters with Dimethylsulf­oxonium Methylide

“…We elected to investigate this observation. As pointed out in a recent essay,8 such unexpected experimental results have played a critical role in the advancement of organic synthesis; one ignores such “outliers” at one's own risk.…”