Light Can Drive Ullmann Reaction - C&EN Global Enterprise (ACS

Nov 4, 2012 - Light exposure can trigger the seminal, 110-year-old Ullmann reaction—which typically forges C–N bonds via heat and a copper complex...
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NEWS OF THE W EEK

PETITIONERS SEEK TO PROTECT EUROPEAN R&D PROACTIVE PROTEST Largest block of petition support is from Spain and Germany.

SCIENCE FUNDING: Scientists lobby to safeguard financial support for research

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ORE THAN 100,000 people have signed a

petition calling on European leaders to shield research funding from austerity measures when the region’s 2014–20 budget is discussed by national leaders at a summit later this month. What could be at risk at the Nov. 22–23 summit is the €80 billion ($104 billion) budget for Horizon 2020, the European Union’s dossier for research and innovation. Horizon 2020 is a new grouping of all R&D programs across the 27 countries that compose the EU. The online petition was launched after an open letter by eminent European scientists in defense of research funding was published on Oct. 23 in newspapers across NOTE: As of Nov. 1. a Includes countries with less than 5% of signatories and the 84 Europe. The letter has now been signed by signatories who did not indicate a country. 44 Nobel Laureates and six Fields Medalists. SOURCE: www.no-cuts-on-research.eu

LIGHT CAN DRIVE ULLMANN REACTION PHOTOCHEMISTRY: New mechanistic

insight into century-old C–N bond formation process

Light, combined with a copper catalyst, drives an Ullmann reaction, forming an arylamine from an aryl halide and an amine.

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IGHT EXPOSURE can trigger the seminal,

110-year-old Ullmann reaction—which typically forges C–N bonds via heat and a copper complex—showing that the reaction can proceed via single-­electron transfer (Science, DOI: 10.1126/ science.1226458). This finding will prompt the design of new ways to leverage this type of coupling reaction, which is widely used to form arylamines from aryl halides and amines for use in pharmaceuticals and materials science. “Now we can design reaction schemes that use the single-electron transfer pathway in Ullmann C–N coupling, and maybe other types of reactions,” says Jonas C. Peters, who performed the study in collaboration with Gregory C. Fu and other colleagues at California Institute of Technology. The work may lead WWW.CEN-ONLIN E .ORG

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“Science can help us find answers to many of the pressing problems facing us at this time: new ways to harness energy, new forms of production and products, improved ways to understand how societies function and how we might order them better,” notes the letter, which was signed by 15 Nobel Laureates in Chemistry, including Gerhard Ertl, Jean-Marie Lehn, and Harold W. Kroto. “In the case of a severe reduction in the EU research and innovation budget we risk losing a generation of talented scientists just when Europe needs them most,” they write. The Nobel Laureates’ letter “acted as motivation to the younger generations to raise their voices too,” says Leif Schröder, secretary for the Young Academy of Europe, a recently formed association of young researchers. The group launched the online petition in collaboration with the Initiative for Science in Europe, an umbrella group for many of the region’s scholarly societies and scientific organizations. The highest number of petition signatories currently comes from Spain. This is likely a reflection of the Spanish government’s austerity cuts to national research funding budgets, which make scientists in that country particularly dependent on European funding, Schröder says. But it’s not just Spain: Researchers in other economically challenged EU countries are also dependent on EU funding to compensate for reduced national research budgets, he says.—SARAH EVERTS

to practical variants of the C–N bond-forming process that work under mild conditions, he says. “It is definitely a major breakthrough in the field of copper catalysis and will undoubtedly break new ground,” says Gwilherm Evano of the Université libre de Bruxelles, in Belgium, who develops natural product syntheses using copper catalysts. UCLA chemistry professor Kendall N. Houk, whose computational studies of the reaction suggested the possibility of a single-electron transfer mechanism, says the new experimental work is “a major advance in a venerable reaction. Everyone in organic chemistry is interested in and puzzled by the mechanism of this process.” The authors designed C–N coupling experiments using both stoichiometric and catalytic amounts of a coppercarbazolide complex and exposure at room temperature to a 13-W compact fluorescent lightbulb or a 100-W mercury lamp. Their results indicate that photons cause the copper complex to transfer an electron to the aryl halide, cleaving the aryl halide’s carbon-halogen bond and producing a radical ion pair, which then leads to C–N bond formation between the aryl halide and carbazole. An alternativepathwaysuggestedfornon-photoinducedUllmann couplings had been that carbon-halide bond breaking occurs during a concerted addition to the copper. “We’re already at work trying to explore how broad the scope of this type of chemistry is,” Peters says.— ELIZABETH WILSON

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