Bill Morandi

Last Name

Morandi

First Name

Bill

ORCID

0000-0003-3968-1424

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09634 - Morandi, Bill / Morandi, Bill

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Publications 1 - 10 of 15

Metal- and CO-Free Carbonylation of Alkyl Iodides
Le Saux, Emilien; Mathis , Maurus; Panizzolo , Giorgia; et al. (2025)
Journal of the American Chemical Society
We report a new method for the carbonylation of alkyl iodides under photochemical conditions. The process relies on a simple aryl formate reagent, synthesized in one step from readily available chemicals and capable of releasing CO along with a phenolate species in the presence of a mild base. The photoactivity of this phenolate is harnessed to activate alkyl iodides via single-electron transfer and generate alkyl radicals that add to CO and ultimately offer access to carboxylic acids and amides. This new, user-friendly procedure overcomes the typical need for CO gas and/or metal catalysts in carbonylation chemistry while being highly efficient and versatile to accommodate a variety of functional groups.
Metal Electronics Mediate Steric and Coordination Number Effects on Palladium(II) C–X Reductive Elimination
Bogdos , Michael K.; Roediger, Sven; Ruepp , Florian; et al. (2025)
Journal of the American Chemical Society
Reductive elimination is the key bond-forming elementary step in many transition metal-catalyzed reactions relevant to the synthesis of pharmaceuticals, materials and fine chemicals. Metal electronics, ancillary ligand sterics and metal complex coordination number have been identified as the primary factors which affect the rate of reductive elimination, but their relative importance has not been quantified. By studying a new class of palladacycles using kinetics, electrochemistry, DFT calculations and tools from causal inference, we reexamine the canonical model and find that a direct effect of coordination number on rate is unlikely. To address this contradiction, we propose an updated understanding based on mechanistic considerations, which accounts for our findings, the canonical understanding, and other observations in literature. Path coefficients calculated using mediation analysis allow the quantification of the effects of electronics, sterics and coordination number on the rate. Overall, we find that electronics and changes in coordination number exert the greatest influence on the rate, with the latter primarily acting through altering metal electronics. Finally, using this new-found knowledge, we were able to use the structures of complexes reported in the literature to calculate appropriate DFT descriptors and build a model capable of predicting the rate of reductive elimination for C–N, C–S and C–O bond formation with reasonable accuracy.
Palladium-Catalyzed Transfer Iodination from Aryl Iodides to Nonactivated C(sp³)–H Bonds
Le Saux, Emilien; Morandi, Bill (2025)
Journal of the American Chemical Society
We report a new strategy for the catalytic iodination of nonactivated C(sp 3)-H bonds. The method merges the concepts of shuttle and light-enabled palladium catalysis to employ aryl iodides as both hydrogen atom transfer reagents and iodine donors. A noncanonical Pd0/PdI catalytic cycle is harnessed to transfer iodine from a C(sp 2) to a C(sp 3)-H bond under mild conditions, which tolerate sensitive functional groups. This mechanism is also applied to implement a C(sp 3)-H thiolation that exploits reversible steps of the system.
Chemodivergent C-to-N atom swap from benzofurans to benzisoxazoles and benzoxazoles
Paschke, Ann-Sophie K.; Schiele, Stefanie; Pinard, Camille; et al. (2025)
Chemical Science
Facile derivatization of biologically active compounds without prefunctionalization expands the chemical space and accelerates the discovery of new molecules. Atom swap reactions have recently emerged as powerful molecular editing tools, yet such reactions remain rare. Herein, we describe a convenient, chemodivergent protocol to perform a net C-to-N atom swap in benzofurans, affording benzoxazoles or benzisoxazoles via a cascade of oxidative cleavage, oxime formation, and cyclization using commercially available reagents.
C-H Functionalization via Single Atom Metathesis of C-H and C-X Bonds
Jankins, Tanner C.; Berger, Barnabé; Aouane, Françoise A.; et al. (2025)
Journal of the American Chemical Society
Metathesis and reversible catalytic reactions are fundamentally intriguing and powerful tools in modern synthetic chemistry. While most reversible catalytic reactions are predicated on breaking and forming reactive functional groups, the ability to leverage the C-H bond as a functional group in metathesis reactions has proved to be exceptionally challenging. Here, we develop a C-H/C-X metathesis reaction through a radical swapping protocol where hydrogen and halogen are traded between molecules via reversible hydrogen atom transfer (HAT) and halogen atom transfer (XAT) that allows for mild C-H halogenation. The reversibility of this process allows for the selective dehalogenation of polyhalogenated products to form monohalogenated products. Leveraging the reversibility of this process, halogenated organic pollutants can also serve as halogen sources for C-H halogenation. In a broader context, this work establishes that incorporating reversible metathesis logic in C-H bond functionalization can provide complementary advantages in synthetic strategies.
Oxidative amination by nitrogen atom insertion into carbon-carbon double bonds
Brägger, Yannick; Paschke, Ann-Sophie K.; Nasiri, Nima; et al. (2025)
Science
The synthesis of nitrogen-containing molecules through carbon-nitrogen (C-N) bond formation is critical for the discovery and preparation of medicines, agrochemicals, and materials. Here, we report the direct insertion of a nitrogen atom into unactivated carbon-carbon double bonds to access aza-allenium intermediates, which can be converted either into nitriles or amidine products, depending on the initial alkene substitution pattern. This operationally simple and highly functionally compatible reaction works on a wide range of unactivated alkenes. PIFA, a commercially available and inexpensive hypervalent iodine reagent, is key to this reactivity. Our mechanistic proposal is supported by chemical trapping experiments, which concomitantly demonstrate the utility of our method to access valuable N-heterocycles. Additionally, our method can be used as a general strategy for synthesizing amides and amines, as well as 15N-labeled molecules.
Shuttle HAT for mild alkene transfer hydrofunctionalization
Jankins, Tanner C.; Blank, Philip M.; Brugnetti, Andrea; et al. (2024)
Nature Communications
Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C-C bonds in organic synthesis. Cobalt hydrides (Co-H) have garnered significant attention in this field, where the weak Co-H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of peroxide oxidant and silane reductant. Here we show that the reverse process of HAT to an alkene, i.e. hydrogen atom abstraction of a C-H adjacent to a radical, can be leveraged to generate catalytically active Co-H species in an application of shuttle catalysis coined shuttle HAT. This method obviates the need for stoichiometric reductant/oxidant mixtures thereby greatly simplifying the generation of Co-H. To demonstrate the generality of this shuttle HAT platform, five different reaction manifolds are shown, and the reaction can easily be scaled up to 100 mmol.
One-Step Process for the Regiodivergent Double Hydrocyanation of 1,3-Butadiene
Long, Jinguo; Wang, Ting; Zhong, Hongyu; et al. (2025)
Angewandte Chemie. International Edition
In industry, the two important nitrile starting materials, adiponitrile and 2-methylglutaronitrile, are primarily manufactured through the well-known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel-catalyzed divergent, one-step double hydrocyanation of 1,3-butadiene to produce either adiponitrile or 2-methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity-determining step. Organometallic studies confirm the formation of well-defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel-catalyzed synthesis of adiponitrile and 2-methylglutaronitrile from butadiene, and it also represents a high-level of catalyst-controlled regioselectivity via the fine-tuning of ligand pocket geometry.
Coupling of unactivated alkyl electrophiles using frustrated ion pairs
Roediger, Sven; Le Saux, Emilien; Boehm, Philip; et al. (2024)
Nature
Cross-electrophile coupling reactions have evolved into a major strategy for rapidly assembling important organic molecules1. Two readily accessible electrophiles are coupled to form new C-C bonds, providing a key advantage over traditional cross-coupling strategies that require the preformation of reactive organometallic species. Yet, the formation of C(sp3)-C(sp3) bonds that form the core of nearly all organic compounds remains highly challenging with current approaches, calling for the design of innovative new strategies. Here we report a distinct, transition-metal-free platform to form such bonds without the need for activating or stabilizing groups on the coupling partners. The reaction is enabled by an unusual single-electron transfer in a frustrated ion pair, and it can couple fragments containing functional groups that would be challenging in related transition-metal-catalysed processes. Moreover, we could further leverage this new mechanistic manifold in the design of other reactions, showing the broad potential of this type of reactivity. We anticipate that our results will provide a framework for further exploration of this reactivity pattern to tackle challenging problems in organic synthesis.
Olefination of Activated Alkyl Halides with Phosphonium Salts
Roediger, Sven; Vieira, Adriana Neves; Brudy, Cosima L.; et al. (2024)
Synthesis
A base-promoted olefination reaction between alkylphos-phonium salts and activated alkyl halides has been developed. Theproducts were obtained in excellent E-selectivity. In contrast to mostother olefination reactions of phosphonium salts, the reaction yieldstriphenylphosphine as the main by-product, which can be directly re-used in the formation of new phosphonium salts.

Publications 1 - 10 of 15

Bill Morandi

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