Dr. Giacomo Crisenza

Paolo Melchiorre Group

Enantioselective photochemical transformations

Giacomo graduated in Chemistry in 2010 from the Università degli Studi in Milan and, in 2012, he obtained his Master’s degree in Organic Chemistry from the same institution. His undergraduate thesis projects were conducted under the supervision of Prof. Dalla Croce and Prof. La Rosa. In October 2012 he joined the Chemical Synthesis CDT programme at the University of Bristol, where he undertook his doctoral studies with Dr John F. Bower. His research focused on the development of novel methodologies for selective C-­C bond formation via C­-H activation. In June 2017, after successfully defending his Ph.D. thesis, he started a postdoctoral appointment in the group of Prof. Paolo Melchiorre at ICIQ in Tarragona, where he is currently investigating enantioselective photochemical transformations. In his spare time outside of the lab, Giacomo enjoys football (both playing and supporting), basketball and an ice-cold beer with friends.

From 01/04/2018 to

31/03/2020

PHOTO ORGANO-Ir CAT

The requirement for drug discovery to facilitate the identification of successful lead candidates has challenged synthetic
chemists to develop innovative strategies to rapidly generate screening collections of chiral molecules. Recently, the
application of asymmetric aminocatalysis to cascade reactions has addressed this target enabling extraordinary levels of
sophistication and stereocontrol, while fulfilling the requirements for both atom and step economy. Because of the rapid
progress achieved, the general perception is that it would be difficult to further expand the synthetic potential of the
aminocatalytic cascade approach. However, recent works from the host´s laboratories demonstrate that, by exploiting the
photochemical activity of organocatalytic intermediates, light irradiation unlocks reaction pathways unavailable in the groundstate domain. In particular, by bringing a catalytically generated iminium ion to an electronically excited state, it is possible to
perform β-functionalisations of enals not achievable under thermal control.
This proposal seeks to capitalise upon this novel reactivity to further expand the synthetic potential of the organocatalytic
cascade technique, by providing new opportunities for reaction invention. We plan to accomplish this by exploiting the
photochemistry of iminium ions in processes that synergistically combine enamine chemistry with transition metal catalysis,
thus merging, for the first time, tandem organo-metal catalysis with asymmetric photoreactions. The planned research
combines perfectly the host´s expertise in photochemical organocatalysis with the fellow´s experience in transition metal
catalysis. These enantioselective cascade reactions will be used for the synthesis of chiral molecules of biological interest.

Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes
Crisenza, G. E. M.; Mazzarella, D.; Melchiorre, P.
J. Am. Chem. Soc. 2020
DOI: 10.1021/jacs.0c01416

Asymmetric Photocatalytic C−H Functionalization of Toluene and Derivatives
D. Mazzarella, G.E.M. Crisenza, P. Melchiorre
J. Am. Chem. Soc 2018, 140, 27, 8439–8443
DOI: 10.1021/JACS.8B05240

Mechanistic Studies in Photocatalysis
L. Buzzetti, G. E. M. Crisenza, P. Melchiorre
Angew. Chem. Int. Ed. 2019, 58 (12), 3730-3747
DOI: 10.1002/anie.201809984.