Research Lines

DESIGN AND DEVELOPMENT OF CATALYTIC SYNTHETIC METHODOLOGIES

ELECTRO-ORGANIC-SYNTHESIS (eChem)

 

Electrosynthesis: employment of electrogenerated radicals of different philicity for multiple synthetically relevant transformations.  

In this emerging research field, we focus on oxidative and reductive protocols for the generation of chemical complexity and diversity.

  • Convenient eChem protocols involved the functionalization of Morita-Baylis-Hillman (MBH) adduct by means of functionalization with electrophilic radicals (Org. Lett. 2022, 24, 4354-4359 [link]).
  • The reductive fixation of CO2 into organic scaffolds is also a common target in our laboratories. Evidence of electrochemical carboxylation of MBH reagents was also recently documented (Synthesis, 2023, 55, 3047-3055 [link]).
  • An electrochemical C-H activation/functionalization of simple ethers was realized by means of a new Radical Active Carbonate (RAC). The site and stereoselective functionalization of MBH adduct is then performed under mild conditions (Chem. Commun. 2023, 59, 2664-2667 [link]).
  • The deeply reductive cyclodimerization of chalcones have been investigate and utilized as platform to exploit the unique “self-adaptability” of galvanostatic electrochemical conditions (Chem. Commun. 2024, 60, 404-407 [link]).

CROSS-ELECTROPHILE COUPLING

 

Nickel catalyzed cross-electrophile coupling: use of redox active nickel complexes for the instauration of cascade skeleton rearrangements starting from readily available building blocks.  

With the employment of readily available and air-stable Ni(II) complexes the realization of polycyclic-fused organic motifs is carried out under reductive conditions. Enantioselection and incorporation of CO2 are value-added aspects of the documented transformations.

 

  • New chiral Ni-complexes were adopted to carry out a cascade enantioselective (ee up to 98%) intramolecular Heck cross-coupling/carboxylation reaction (Chem.Eur.J. 2021, 27, 7657-7662. [link]).
  •  A new radical-based strategy to synthetize α-aryl-α-trifluoromethyl alcohols is proposed via Ni-assisted radical generation/rearrangement/trapping of a trifluoethyl-based radical-active-ether. Large scope and mechanism rationalization fulfill the investigation (Angew. Chem. Int. Ed. 2022, e202211732 [link]).
  • The cross-electrophile coupling catalyzed by Ni was also coupled with CO2 fixation and C-C cleavage steps. The cascade procedure resulted in the formation of synthetically benzofused scaffolds. The synergistic action of Ni catalysis and AlCl3 was discovered (Chem. Commun. 2022, 58, 4071-4074 [link]).
  • A double incorporation of CO2 was realized in a sequential carbonylation/carboxylation reaction promoted by Ni catalysis. The role of AlCl3 in triggering CO2 activation and as well as oxygen scavenger id disclosed via a dedicated mechanism investigation (Org.Lett. 2023, 25, 6969-6974 [link]).

 

HOMOGENEOUS GOLD CATALYSIS

 

Homogeneous gold catalysis: the development of innovative electrophilic activations of unsaturated hydrocarbons and the realization of new organic ligands enabled obsolete organic transformations to be replaced by modern and sustainable alternatives.  

The exploitation of week secondary interactions was recently targeted for the fin-tuning of organo-gold complexes as catalysis in organic reactions.

  • A new class of ImPy carbene ligands were developed proving enhanced reactivity profile with respect to conventional ligands in numerous cascade reactions (ACS Org. Inorg. Au, 2022, 2, 229-235. [link]). This impact was rationalized as an activating electrophilic character of the organogold species intermediates.
  • This new class of ligands was successfully applied to the synthesis of intramolecular hydrocarbonylation of allenes to deliver N(1)-C(2)-fused oxazino-indolones in straightforward manner (Chem. Commun. 2022, 58, 8698-8701) [link]).
  • The accelerating effect of EWGs on organic ligands was recently extended to phosphine ligands. A new version of the C1-symmetric phosphine, namely: PedroPhos was synthetized, fully characterized, and tested in organic reactions involving alkynes activations (submitted).

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