Catching Breslow Intermediates - C&EN Global Enterprise (ACS

Oct 29, 2012 - Everyone who works with these types of carbenes believes they exist, Bode says. The field's foundations rely on the existence of these ...
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NEWS OF THE W EEK

THIRD DEBATE STRAYS OFF TOPIC POLITICS: Economy, not foreign policy,

dominates presidential face-off

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about foreign policy, President Barack Obama and his Republican challenger, Mitt Romney, repeatedly steered the conversation toward strengthening the U.S. economy and maintaining U.S. competitiveness. And although the candidates briefly revisited their plans for energy and education policy to accomplish these goals, support for basic science funding was also part of the mix. The President mentioned the importance of R&D funding to economic growth and global competitiveness at least four times during the 90-minute debate. For example, he said, “If we don’t continue to put money into research and technology that will allow us to creROBERT DUYOS/MCT/NEWSCOM

Romney (left) and Obama met for one last debate at Lynn University in Boca Raton, Fla., on Oct. 22.

N WHAT WAS supposed to be a presidential debate

CATCHING BRESLOW INTERMEDIATES CARBENES: By tuning reactivity,

chemists obtain firm evidence for key reactive species

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54-YEAR QUEST for carbene chemists just

took a big step toward resolution: German researchers say they’ve generated and characterized elusive Breslow intermediates, which are crucial players in biochemistry and catalysis (Angew. Chem. Int. Ed., DOI: 10.1002/anie.201205878). “The Breslow intermediate is the Higgs boson of the N-heterocyclic carbene catalysis field,” says Jeffrey W. Bode of ETH Zurich, who was not involved in the work. Columbia University’s Ronald Breslow first proposed the intermediates that bear his name in 1958, when he suggested that thiamine-mediated reactions in biochemistry hinge on carbene reactivity. Every­one who works with these types of carbenes believes they exist, Bode says. The field’s WWW.CEN-ONLIN E .ORG

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ate great businesses here in the U.S.,” the country will lose its competitive edge to nations such as China. Former Massachusetts governor Romney mentioned basic research funding once, but not as a means to foster competitiveness or economic prosperity. Instead, he brought it up to make the point that such funding should go to universities, not companies. “Research is great,” he said, but the federal investment in companies such as Tesla or Fisker to develop electriccar batteries isn’t basic research. He added that, if elected, he would end such federal investments. The debate also touched on the looming governmentwide budget cuts known as sequestration that are set to take place on Jan. 2, 2013. Romney made it clear that he would protect military spending from these cuts, which are the mandated results of Congress’ failure to reach agreement on cutting the federal budget deficit. But the President went further on the subject of sequestration. He stated emphatically: “It will not happen.” His confidence may indicate that he has a plan to break Congress’ impasse on the issue. Romney outlined a plan that he said would get the U.S. to a balanced budget in eight to 10 years. First, he said, he would immediately put in place a 5% cut to all nondefense discretionary federal spending. Then, he continued, he would get rid of programs “that we don’t absolutely have to have” and shift control of other federal programs to states.—SUSAN MORRISSEY

foundations rely on the existence of these intermediates, he adds, but they have never been isolated. Albrecht Berkessel of the University of Cologne and colleagues made their intermediates by combining aromatic aldehydes with a saturated carbene. They surmised that their carbene catalysts were sufficiently slow to make intermediates detectable. “We were lucky enough to hit the sweet spot,” Berkessel says. Their intermediates are stable enough to be characterized but reactive enough to behave as expected by NMR. “We’ve seen hints of the Breslow intermediate before,” Bode says, but this report “is the first to conclusively capture it.” As with the Higgs boson, chemists will disagree whether the intermediates have now really been cornered, warns Karl A. Scheidt of Northwestern University. Most of the new intermediates lack a sulfur atom and are not fully aromatic as Breslow proposed, he says. However, this work “is an important step forward” and should be taken together with reports of deoxy, methylated, and nitrogen Breslow analogs detected earlier this year by groups at Colorado State University and the University of Munich. Together, Scheidt says, the studies are “an excellent foundation” for understanding carbenes’ versatility. “This nice piece of work shows you can get a species that’s very closely related to what I proposed and look at its properties,” Breslow says. Berkessel is a former postdoc, he says, “and I’m proud of the guy.”— CARMEN DRAHL

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