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Robert Stockman

Professor of Organic Chemistry, Faculty of Science

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Biography

Having completed a PhD at Bristol (working for Tim Gallagher) in 1997 and a postdoctoral fellowship at the University of Texas at Austin (working for Philip Magnus, FRS), Robert Stockman started his independent career at the University of East Anglia in 1999, where he initiated a number of projects aimed at the use of novel heterocyclic chemistry within the context of the total synthesis of biologically important natural and un-natural products. In April 2007 he was awarded an EPSRC Advanced Research Fellowship and was promoted to Senior Lecturer at UEA. In September 2007 he joined the University of Nottingham as Associate Professor of Organic Chemistry, and was promoted to Associate Professor and Reader in 2010, and to full Professor in 2016.

Research Summary

Research Areas:

1. Development of New Synthetic Methods

S(IV) and S(VI) Chemistry: Since our first publication in the area in 2004, the Stockman Group have developed a significant and influential body of work in the area of sulfur (IV) and sulfur (VI) chemistry. This work includes the first asymmetric synthesis of vinyl aziridines using sulfinimines; a highly practical and cost-effective one-pot methodology for the synthesis of sulfinimines using a novel four-component coupling methodology which incorporates a wide range of groups not only on the carbon, but also the sulfur of the sulfinimine with exquisite stereocontrol. We then extended this chemistry to a general multi-component one-pot asymmetric synthesis of chiral amines from aldehydes requiring no chromatography. We published on the utility of S-mesitylsulfinimines as highly effective alternatives to the Ellman tert-butylsulfinimines for the synthesis of highly sterically congested chiral amines with exceptional stereocontrol. Further exploring the reactivity of sulfinimines, we disclosed the first general asymmetric cycloadditions of sulfinimines and the first asymmetric radical cyclisations of sulfinimines, which gave extremely high levels of diasterocontrol (>98% de). In other sulfur (IV) work, we published the first X-ray structure of a non-cyclic vicinal disulfoxide (dispelling the long-held notion these did not exist, and providing the first data for the S-S bond lengths in for a linear disulfoxide), and detailed a palladium-catalysed asymmetric allylation of sulfinimines using simple non-chiral ligands (collaboration with Yang). We have also developed a versatile one-step synthesis of chiral cyclic sulfoximines (highly topical chemotype in drug discovery) from sulfinimines (via vinyl aziridine intermediates) utilising a new sigmatropic rearrangement, and a transition-metal free stereospecific Sp2-Sp3 C-C coupling utilising hypervalent sulfur. Initial work in the area of sulfur (VI) chemistry involved the simple synthesis of sulfonimidamides from sulfinamides using Bull's nitrene transfer chemistry, and a thorough investigation into the N-functionalisation of the NH sulfonimidamides to a wide range of acyl, aryl and alkyl sulfonimidamides and an investigation of their potential for medicinal chemistry in terms of their pharmacokinetic profile. We have followed this up with a general synthesis of sulfoximines through C-S coupling of sulfonimidates with Grignard reagents, and recently one of the first asymmetric formations of sulfoximines using a similar approach using chiral cyclic sulfoximidate templates.

2. Total Synthesis of Complex Natural Products.

A second research theme is combining bi-directional synthesis and tandem reactions to generate routes to complex molecules that are direct and generate complexity in the most efficient manner possible. To date these studies have resulted in the concise total syntheses of several natural products, and in the concise generation of a range of three-dimentional scaffolds which have been used to produce libraries for screening within the European Lead Factory.

3. Monomers From Sustainable and Renewable Sources.

In collaboration with Profs Steve Howdle, Derek Irvine, Stephen Harding, Cameron Alexander, we are using our know-how of functional group chemistry to generate a range of monomers from sustainable feedstocks - nost notably, terpenes. Our collaborators then utilise these in a wide range of polymerisation applications.

Selected Publications

  • MONAGHAN, OLIVIA R., SKOWRON, STEPHEN T., MOORE, JONATHAN C., PIN-NO, MARIA, KORTSEN, KRISTOFFER, ATKINSON, RACHEL L., KRUMINS, EDUARDS, LENTZ, JOACHIM C., MACHADO, FABRICIO, ONAT, ZEYNEP, BROOKFIELD, ADAM, COLLISON, DAVID, KHLOBYSTOV, ANDREI N., DE FOCATIIS, DAVIDE, IRVINE, DEREK J., TARESCO, VINCENZO, STOCKMAN, ROBERT A. and HOWDLE, STEVEN M., 2022. A self-crosslinking monomer, alpha-pinene methacrylate: understanding and exploiting hydrogen abstraction POLYMER CHEMISTRY. 13(39), 5557-5567
  • MATOS, PRISCILLA MENDONCA, LEWIS, WILLIAM, ARGENT, STEPHEN P., MOORE, JONATHAN C. and STOCKMAN, ROBERT A., 2020. General Method for the Asymmetric Synthesis of N-H Sulfoximines via C-S Bond Formation ORGANIC LETTERS. 22(7), 2776-2780
  • DEAN, W. M., SIAUCIULIS, M., STORR, T. E., LEWIS, W. and STOCKMAN, R. A., 2016. Versatile C(sp(2))-C(sp(3)) Ligand Couplings of Sulfoxides for the Enantioselective Synthesis of Diarylalkanes Angewandte Chemie-International Edition. 55(34), 10013-10016

Centre for Cancer Sciences

The University of Nottingham
Centre for Biomolecular Sciences
Nottingham, NG7 2RD


telephone: +44 (0) 115 823 1546
email: MS-CCS@nottingham.ac.uk