Nobel Connection
2010 Nobel news connects with Oswego chemistry grads

“Not everybody gets to say that they worked with a Nobel Prize winner,” said SUNY Oswego master’s graduate Michael Plante. He is one of over a dozen chemistry students of Augustine Silveira at Oswego from the 1970s to 1990s who can, as of this month, say just that.

When the Royal Swedish Academy of Sciences announced Oct. 6 that Ei-ichi Negishi and two colleagues had won the 2010 Nobel Prize in Chemistry, excitement surged through the network of Oswego alumni around the country.

Emeritus Professor Augustine Silveira.Silveira, distinguished teaching professor emeritus of chemistry at Oswego, began collaborating with Negishi, now the Herbert C. Brown distinguished professor of organic chemistry at Purdue University, in the early 1970s when 2010 Nobel laureate was an assistant professor at Syracuse University and Silveira was an associate professor at Oswego.

They both engaged their students in their collaborative projects and co-authored papers with them that became part of the overall package that the Nobel honored this month, Silveira said.

Their research involved using the metallic element palladium as a catalyst to synthesize complex carbon-based molecules. The Royal Swedish Academy of Sciences called that “one of the most sophisticated tools available to chemists today and one that is used by researchers worldwide and in commercial production of pharmaceuticals and molecules used to make electronics.”

Inspirational hard work

“We’re all excited about it,” said Plante, now a vice president with Emerson & Cuming Microwave Products in Massachusetts and studying in Harvard Business School’s general management program. When Plante received his master’s degree in chemistry from Oswego in 1976, Negishi traveled to Oswego to sit in on his oral defense of his master’s thesis. “He was inspirational,” Plante said.

Plante was the second Oswego student working with Silveira who collaborated with Negishi. He said he was particularly thrilled by the Nobel news because he saw an interview in which Negishi said the award was based on a core of research done from 1976 to 1978. Plante is the co-author—with Negishi, Silveira and another student, K. W. Chiu—of a paper that came out in 1976 in the Journal of Organometallic Chemistry.

Silveira’s and Negishi’s collaboration extended for more than 20 years, involved Silveira’s students at Oswego and Negishi’s students and post-doctoral fellows at Syracuse and Purdue universities, and led to at least 11 jointly authored research publications.

Jeff Evans of Manlius, a 1986 Oswego graduate who was a graduate research assistant under Silveira from 1986 to 1988, worked in Negishi’s lab at Purdue part of the time. “My whole research program was a collaborative effort with Dr. Negishi on palladium cross-coupling reactions, which is what Dr. Negishi got his award for,” Evans said.

Evans, who earned his doctorate at Syracuse University, left a career at Bristol-Myers Squibb in 2003 to found and develop a pharmaceutical consultancy, Rondaxe, and is now launching a biotechnology firm, Oncoholdings, in Syracuse that will help develop drugs to fight cancer.

Joseph Smith, a native of Oswego and 1984 Oswego graduate who is now a professor of chemistry at Cabrini College near Philadelphia, recalled the details of his graduate work in Silveira’s lab that contributed to a paper in the Journal of Organic Chemistry. He gave a presentation on it at Quest, the college’s research symposium, as a graduate student in 1986: “The Synthesis of Disubstituted Cyclobutenes via the Palladium Catalyzed Cross-coupling Reaction.”

Caring professor

Silveira is enormously proud of his students. “The fact that SUNY Oswego students were very capable of doing Nobel Prize quality research work speaks volumes about the caliber of our students and the quality of Oswego’s chemistry program, past and present,” he said. Evans added, “He is a shameless promoter of Oswego, shameless!”

But Silveira’s students have equally high praise for their organic chemistry professor. “What a dynamic guy!” Plante said. “If you were going to work with him, you were going to work hard.”

And Evans: “He is the most giving person. Gus always put his students first in everything he did in his life. He could have won a Nobel Prize but he’s more about developing people. . . . He has contributed so much to both the scientific and business worlds. All of his students have been immensely successful.”

Citing a number of fellow former students who have established careers and reputations in the biotechnology field, Evans said, “The talent that came out of Oswego is amazing.”

Silveira was the recipient of more than 50 national awards in recognition of his chemistry teaching and research work with his students and his community service during his 38-year career at Oswego.

Ongoing relationship

Silveira and Negishi last co-authored a paper in 1996 and have stayed in touch since Silveira’s retirement in 2000.

Earlier this year, Negishi received the American Chemical Society award for Creative Work in Synthetic Organic Chemistry at the National ACS meeting in San Francisco. Silveira attended the dinner to celebrate the occasion with his wife, Beverly. He said he was pleased to see many of his Oswego students cited and acknowledged for their work, some of which involved palladium-catalyzed cross coupling.

“I cherish our friendship of many years,” Silveira said. After the announcement of the Nobel Prize to Negishi, together with Richard F. Heck of the University of Delaware in Newark and Akira Suzuki of Hokkaido University, he said, “Dr. Negishi spoke with me on the phone . . . and expressed a similar feeling about our relationship.”

Former Oswego students who worked with Silveira and Negishi on research papers included Anthony O. King, who graduated in 1975; Michael Plante, 1976; Louis F. Valente, 1977; Frank J. Villani Jr., 1978; Frank Dipasquale, 1979; William Patterson, 1980; Anthony Pecora, 1980; Mark Reeves, 1982; Steven C. Orlando, 1982; Joseph Smith, 1984; and Jeffrey Evans, 1986. Also working on the research were former Oswego students Bair L. Chiou, Henry D. Bretherick Jr. and Ronald P. Schreck.

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Research papers jointly authored by Negishi, Silveira and SUNY Oswego students (names bold faced) from 1975 to 1996, from List of Publications by Ei-ichi Negishi:

“A General One-Carbon Homologation of Organoboranes via α Thioorganoborate Anions”
Negishi, E.; Yoshida, T.; Silveira, A. Jr.; Chiou, B. L.
J. Org. Chem. 1975, 814-816.

“An Unusually Facile Dehydroboration of Triorganoboranes Formed by Treatment of Alkenyltrialkylborates with Hydrochloric Acid”
Chiu, K. W., Negishi, E.; Plante, M. S.; Silveira, A. Jr.
Organometal. Chem. 1976, 112, C3-C6.

“A General Synthesis of Terminal and Internal Arylalkynes by the Pd-Catalyzed Reaction of Alkynylzinc Reagents with Aryl Halides”
King, A. O; Negishi, E.; Villani, F. J., Jr.; Silveira, A., Jr.
J. Org. Chem. 1978, 43, 358-360.

“Scope of the Reaction of Organoborates with Organolithiums as a Method of Preparation of Lithium Organoborates. Stability of Lithium Organoborates”
Negishi, E.; Idacavage, M. J.; Chiu, K. W.; Yoshida, T.; Abramovitch, A.; Goettel, M. E.; Silveira, A., Jr.; Bretherick, H. D.
J. Chem. Soc., Perkin II. 1978, 1225-1232.

“A Highly Selective Method for α-Alkylation of Ketones via Potassium Enoxytrialkylborates”
Negishi, E.; Idacavage, M. J.; Dipasquale, F.; Silveira, A., Jr.
Tetrahedron Lett. 1979, 845-848.

“NMR Determination of n-Butyllithium.”
Silveira, A., Jr.; Bretherick, H. D., Jr.; Negishi, E.
J. Chem. Educ. 1979, 56, 560.

“Conversion of Methyl Ketones into Terminal Acetylenes and (E)-Trisubstituted Olefins of Terpenoid Origin”
Negishi, E.; King, A. O.; Klima, W. L.; Patterson, W.; Silveira, A., Jr.
J. Org. Chem. 1980, 45, 2526-2528.

“A Selective and Efficient Synthesis of (E)-4-Methyl-3-alken-1-ols via Zirconium Catalyzed Carboalumination of Terminal Alkynes”
Kobayashi, M.; Valente, L. F.; Negishi, E.; Patterson, W.; Silveira, A., Jr.
Synthesis 1980, 1034-1035.

“1,4- and 1,5-Diketones via Palladium-Catalyzed Allylation of Potassium Enoxyborates”
Negishi, E.; Luo, F. T.; Pecora, A. J.; Silveira, A., Jr.
J. Org. Chem. 1983, 2427-2429.

“Synthesis of Benzofurans, Tetrahydrobenzofurans, and Related Cyclic Ethers via Cyclic Carbopalladation”
Negishi, E.; Nguyen, T.; O’Connor, B.; Evans, J. M.; Silveira, A., Jr.
Heterocycles, 1989, 28, 55-58.

“Convenient and General Synthesis of 1-Monoorganyl- and 1,2,-Diorganylcyclobutenes via Cyclialkylation”
Negishi, E.; Liu, F.; Choueiry, D.; Mohamud, M. M.; Silveira, A. Jr.; Reeves, M.
J. Org. Chem., 1996, 61, 8325-8328.

(Posted: Oct 25, 2010)