Catalytic Addition: Aromatic Amines Plus Aromatic Olefins - C&EN

Nov 12, 2010 - Chemistry professor John F. Hartwig and postdoc Motoi Kawatsura report ... hydroaminations as a graduate student with professor Tobin J...
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ern University. 'There are intramolecular versions of Enantioselective catalyst yields this reaction that work optically active amine well," he adds, "but the intermolecular variant is one of the most challenging problems in homogeneous catalysis, and catalytic solutions are rare." (fl)-BINAP-Pd(OS02CF3)2 Hartwig and Kawatsura, who is now at Merck in 25 °C ' FoC Rahway, N.J., developed their palladium catalysts BINAP = 2,2-bis(diphenylphosphino)-1,1-binaphthyl by following a lead from high-throughput screenAs simple as it sounds, an efficient way ing studies they had carried out to look tween catalyst activity and ligand structo add amines to olefins has eluded for the best catalytic system for the ad- ture. With better understanding, they chemists for years. Yale University re- dition of aniline to dienes. hope to find systems that will work with searchers have now devised a catalytic "Motoi was absolutely amazing in a- and ^-substituted styrenes and aliphatsystem that gives good yields of the in- his tenacity," Hartwig tells C&EN. ic substrates. They also plan to select and termolecular addition products of aro- "When he told me he obtained 90% construct ligands that may increase the matic amines and aromatic olefins and yield for the addition of aniline to sty- scope of the asymmetric additions. that can even work enantioselectively. rene, I thought he was joking with me, "Researchers have been trying for Chemistry professor John F. Hartwig because I had told him that I kept more than 30 years to construct sysand postdoc Motoi Kawatsura report dreaming at night of amines adding to tems for hydroamination," Hartwig that palladium species catalyze intermo- olefins. But he was serious and found says. "I think weVe uncovered a catalyst lecular hydroamination in the presence conditions for both fast rates and, in combination that is certainly an integral part of the solution, but it will be some of acid cocatalysts \J. Am. Chem. Soc, some cases, good enantioselectivity." 122, 9546 (2000)]. Although efficient Hartwig's group at Yale currently is time before we know whether it's the intramolecular systems have been conducting mechanistic studies on the keystone weVe put in place." known for some time, the Yale chemists process and defining the relationship bePamela Zurer appear to have developed the first practical catalytic process that doesn't require the amine and olefin to be part of the same molecule. 'This paper by Hartwig is the best ad- Taiwan's Formosa Plastics Group has con- I China. The company, however, says vance in intermolecular olefin hydroami- firmed that, during a visit to China last that most of these reports, some of them nation research yet," notes Michel R. month, company Chairman Wang Yung- quite detailed, are pure fabrications. Gagne, assistant professor of chemistry ching signed at least one letter of intent to Formosa's ability to rapidly expand opat the University of North Carolina, Chap- invest in petrochemical plants in China erations in China is formidable. Over the el Hill. Gagne studied metal-catalyzed hyThere are few details concerning the past few years, it has invested several bildroaminations as a graduate student with content of the letter of intent. "Only he lion dollars in power plants in China, professor Tobin J. Marks at Northwest- knows what was signed," a Formosa which are now operational. The group Plastics spokesman says. has just boosted its engineering knowIn an interview with Taipei's Economic how with the construction of the $10 bilDaily News, Wang said he signed two let- lion Mailiao petrochemical complex that ters of intent. One letter was signed with is nearing completion in Taiwan. Much of the government of Fujian province and the construction work at the complex was concerns possible investment at the Hai- performed by Formosa Group subsidiarcang petrochemical district, an industrial ies. Moreover, Taiwan shares a common area under development near the city of cultural heritage with the east coast of Xiamen. The other letter of intent was China, particularly Fujian province. Thus, signed with the municipal government of conducting negotiations in China is easiNingbo, Zhejiang province, and concerns er for Formosa executives than other forpossible investments in the Meishan Is- eign company executives. land areas. Formosa officials have conObservers familiar with Formosa say firmed that investments in a polyvinyl the company is now eager to expand in chloride plant in the Ningbo area are like- China. In Taiwan, costs are high and enly to proceed first vironmental concerns make it difficult to obtain government approvals to build Taiwan's Chinese-language business Notebooks on shelf above Kawatsura new facilities. press has been running stories since (right) contain records of some 4,000 July about Formosa's intentions to inIn September 1998, Formosa Plastics experiments, "most of them on our way to vest in various petrochemical projects in I President C. T. Lee told C&EN that obhydroamination," according to Hartwig (left).

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Catalytic Addition: Aromatic Amines Plus Aromatic Olefins

Formosa Plastics Set To Build Complex In China

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