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ERC

LAB-SMART Report Summary

Project ID: 305868
Funded under: FP7-IDEAS-ERC
Country: United Kingdom

Final Report Summary - LAB-SMART (Lewis Acidic Borocations: improving Suzuki couplings, Material synthesis, Alkylation and Radical Transformations)

This ERC Starter Grant was focused on utilising inexpensive, low toxicity and earth abundant compounds to achieve two key overarching goals:

(i) to develop new routes to a range of useful organo-boron compounds
(ii) to develop new carbon-carbon bond forming reactions

Organo-boron compounds are extremely useful in chemical synthesis and are ubiquitous in industry and academia due in part to the power of the Nobel prize winning Suzuki-Miyaura reaction which utilises organo-boron compounds as key precursors. The Suzuki-Miyaura reaction enables the facile construction of carbon-carbon bonds and thus provides access to a range of important pharmaceuticals, agrochemicals and organic electronic materials. However, the scope of the Suzuki-Miyaura reaction often is limited by the range of organo-boron compounds that are readily accessible. Therefore one key goal of this research project was to develop new synthetic routes to new organo-boron compounds and more simple synthetic routes to established organoboron compounds. Throughout this project this was achieved without utilising expensive, scarce and toxic precious metals (which dominate most other recently developed routes to organoboron compounds). Instead this project utilised only simple and inexpensive boron electrophiles to develop novel routes to organo-boron compounds, this includes multiple examples that were highly modular and thus provide access to many new organo-boron compounds. These new methodologies has increased the range of organo-boranes that can be simply accessed, thus facilitating the exploration of compound space via the Suzuki-Miyaura reaction and other established chemical transformations that utilise organo-boron compounds as key precursors.

Organo-boron compounds are not only useful as intermediates (e.g. in C-C bond formation), they have recently been established as useful compounds in their own right in part due the modulation of key optoelectronic properties of organic materials on borylation. As part of this project we used simple, precious metal free methodologies to transform organic materials by incorporating a boron moiety. This led to borylated materials with multiple desirable properties, the one most explored to date being the ability to transform compounds that emit in the green/yellow region of the spectrum to ones that emits in the far red / near infra-red region of the spectrum on borylation. These new borylated compounds are stable, have low toxicity and are highly emissive in the solid state even in the far-red/near infra-red region of the spectrum and thus have applications, including in bio-imaging. Borylated compounds from this project have been demonstrated to be as, or more, effective than established bio-imaging agents (based on signal to background ratio for emission at 820 nm – a region where human tissue has good transparency).

This project also developed novel routes to form carbon-carbon bonds which do not rely on toxic, precious metals (for example, most Suzuki-Miyaura coupling reactions require palladium or nickel catalysts which have stringent exposure limits due to their significant toxicity to humans). Instead we have used low toxicity, earth abundant metals to form C-C bonds, in this case C-C bond formation is mediated only by organozinc compounds. Zinc has low toxicity to humans and is relatively abundant (compared to palladium) and inexpensive, thus the development of stoichiometric and catalytic in zinc (thus reducing waste) procedures to form carbon-carbon bonds as developed in this work is notable and offers an alternative to methods using more toxic metals. This new methodology was also demonstrated to be highly modular in terms of the organic electrophile, thus is potentially a versatile new way to make carbon-carbon bonds.

Reported by

THE UNIVERSITY OF MANCHESTER
United Kingdom
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