Catalysis

The Morandi group works on a broad scope of different catalytic reactions. Some of our main focuses are described below.

Shuttle catalysis/Metathesis reactions

Our group has been interested in developing catalytic reversible reactions as a powerful tool to enable both functionalization and defunctionalization reactions. While shuttle catalysis usually refers to the transfer of a small molecule (e.g. HCN, HBr, or Br₂) from a donor to an acceptor molecule, metathesis reactions describe the exchange of functional handles (e.g. –SMe and –CN exchange). These developed reactions are generally useful when the use of commonly toxic reagents, such as HCN, CO, HBr, or Cl₂ can be avoided using this shuttle approach. Additionally, they provide new approaches for the recycling of wastes.

Selected publications:

Merging shuttle reactions and paired electrolysis for reversible vicinal dihalogenations (Science 2021 external pagedoi)
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers (JACS 2021 external pagedoi)
Catalytic isofunctional reactions – expanding the repertoire of shuttle and metathesis reactions (ACIE 2019 external pagedoi)

Amination

Our group is also investigating methods to forge C–N bonds and thereby focuses on directly introducing the amino group as free amine. Obviating protecting group strategies increases step-efficiency, as well as the functional group tolerance since tedious deprotection steps can be avoided. We aim to transform both renewable feedstock chemicals and late-stage targets alike by applying catalytic systems based on benign iron catalysts. A central element in our studies is the use of stable O-substituted hydroxylammonium salts as amino source.

Selected publications:

Hydroxylamine-derived Reagent as a Dual Oxidant and Amino Group Donor for the Iron Catalyzed Preparation of Unprotected Sulfinamides from Thiols (ACIE 2021 external pagedoi)
Direct Synthesis of Unprotected 2-Azidoamines from Alkenes via an Iron-Catalyzed Difunctionalization Reaction (JACS 2020 external pagedoi)
Direct and Practical Synthesis of Primary Anilines through Iron-Catalyzed C–H Bond Amination (ACS Catal. 2016 external pagedoi)

Alkene/alkyne functionalization

The ability to functionalize unsaturated C–C bonds is key to the importance of catalysis in society. The ability to rapidly increase molecular complexity, typically with excellent atom economy, is a core tenant of this chemistry. These functionalization reactions are used on both large scale such as hydroformylation, which is performed on millions of tons per year, for the preparation of commodity chemicals and precursors to milligram scale in the preparation of bioactive compounds.
Our group investigates new ways to functionalize unsaturated C–C multiple bonds, using the power of catalysis. So far, this work has resulted in a variety of discoveries such as carboformylation and the addition of R–X (X= I, COCl) across π-bonds.

Selected publications:

Palladium-Catalyzed Carbothiolation of Alkenes and Alkynes for the Synthesis of Heterocycles (ACS Catal. 2022 external pagedoi)
Palladium-catalysed carboformylation of alkynes using acid chlorides as a dual carbon monoxide and carbon source (Nat. Chem. 2021 external pagedoi)
Catalytic Carbochlorocarbonylation of Unsaturated Hydrocarbons via C–COCl Bond Cleavage (ACIE 2021 external pagedoi)

C-O activation

Due to the importance of those reactions in biomass valorization as well as target-oriented synthesis, we have explored the possibility to activate strong C-O bonds using catalysis.

Selected publications:

Catalytic disproportionation via carbonate redox tags – a unified strategy for mild hydrogenolysis and oxidations of C–O bonds (ChemRxiv 2022 external pagedoi)
Non-innocent electrophiles unlock exogenous base-free coupling reactions (Nat. Cat. 2022 external pagedoi)
Boron-Catalyzed Regioselective Deoxygenation of Terminal 1,2-Diols to 2-Alkanols Enabled by the Strategic Formation of a Cyclic Siloxane Intermediate (ACIE 2015 external pagedoi)