Gold‐Catalyzed Reactions Towards Diversity: From Simple Substrates to Functionalized Carbo‐ and Heterocycles

Abstract

The field of gold catalysis has been in constant expansion during the last twenty years. Based on the precept of π‐activation of unsaturated simple substrates, several new rearrangements have been discovered, implying aryl, alkyne, alkene or keto derivatives as key partners. In this personal account, the main contributions in the field of gold catalysis from our group will be highlighted, emphasizing the recent reports, starting from 1,6‐ and 1,5‐enynes and then moving to keto‐ynes derivatives. The gold‐catalyzed reactions will be presented starting from classical skeletal rearrangements (cycloisomerization) and then domino processes. In each part, the presentation of asymmetric versions will be highlighted.

De‐Novo Design of pre‐miR‐21 Maturation Inhibitors: Synthesis and Activity Assessment

“…Leaning on the broader definition of the privileged scaffold and taking into account the reported RNA binders, [17a–b] we anticipated that the 2‐amino‐dihydropyrrolopyridine could be a valuable scaffold to construct a new library, able to interact with the target using the two most favorable interactions found in RNA binders, that is, hydrogen bonds and π‐stacking interactions [17,18] . In our continuous research programs towards the preparation of bioactive molecules, [19a–c] and our deep experience in sustainable chemistry, we selected the bicyclic scaffold of dihydropyrrolopyridine, which to the best of our knowledge, has never been envisaged as an RNA binder.…”

Phosphorous NMR Analysis and Activity of Chiral BINAP‐Silver Complexes

“…Following our interests in gold [18][19][20][21][22] and silver-catalyzed reactions [23][24][25] and inspired by the work from Koo's group, [26] we envisaged that a silver catalyst could promote an intramolecular [4 + 2] cycloaddition of amide-1,6-enynes. [18] Our preliminary results on the racemic as well as asymmetric intramolecular [4 + 2] cycloaddition process in the presence of Ag-salts and chiral diphosphine ligands led to the synthesis of 2,3,3a,4tetrahydro-1H-benzo[f]isoindol-1-ones (Scheme 1c).…”

Fluorinated Biphenyl Phosphine Ligands for Accelerated [Au(I)]-Catalysis

“…As expected, all crystals obtained showed the common P–Au–Cl linear architecture, lying almost parallel to the outer arene (Au–P–C–C dihedral angles = 0–11.0°, where C–C is the bond connecting the two aromatic rings). The resulting Ar F ···Au interactions turned out to be stronger, with consequent shorter Ar F ···Au contacts ( Cat1 and Cat3 , entries 1 and 2) in comparison to electron-neutral structural analogous JohnPhosAuCl (entry 3).…”