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Ei-ichi Negishi

Ei-ichi Negishi (根岸 英一, Negishi Eiichi, July 14, 1935 – June 6, 2021) was a Japanese chemist who was best known for his discovery of the Negishi coupling.[2][3] He spent most of his career at Purdue University in the United States, where he was the Herbert C. Brown Distinguished Professor and the director of the Negishi-Brown Institute.[4] He was awarded the 2010 Nobel Prize in Chemistry "for palladium catalyzed cross couplings in organic synthesis" jointly with Richard F. Heck and Akira Suzuki.[5]

Ei-ichi Negishi
根岸英一
Negishi in 2010
Born(1935-07-14)July 14, 1935
Xinjing, Manchukuo
(modern Changchun, China)
DiedJune 6, 2021(2021-06-06) (aged 85)
Indianapolis, Indiana, U.S.
NationalityJapanese[1]
Alma materUniversity of Tokyo
University of Pennsylvania
Known forNegishi coupling
ZACA reaction
SpouseSumire Suzuki (m. 1959; died 2018)
Children2
AwardsSir Edward Frankland Prize Lectureship (2000)
Nobel Prize in Chemistry (2010)
Person of Cultural Merit (2010)
Order of Culture (2010)
Scientific career
FieldsChemistry
InstitutionsTeijin
Purdue University
Syracuse University
Hokkaido University
ThesisBasic cleavage of arylsulfonamides, the synthesis of some bicyclic compounds derived from piperazine which contain bridgehead nitrogen atoms. (1963)
Doctoral advisorAllan R. Day
Doctoral studentsJames M. Tour

Early life and education

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Negishi was born in Xinjing (today known as Changchun), the capital of Manchukuo, in July 1935.[6][3] Following the transfer of his father who worked at the South Manchuria Railway in 1936, he moved to Harbin, and lived eight years there.[7] In 1943, when he was nine, the Negishi family moved to Incheon, and a year later to Kyongsong Prefecture (now Seoul), both in Japanese-occupied Korea. In November 1945, three months after World War II ended, they moved to Japan.[3] Since he excelled as a student, a year ahead of what would have been his graduation from grammar school, he was admitted to an elite secondary school, Shonan High School.[8] At the age of 17, he gained admission to the University of Tokyo. After graduation from the University of Tokyo in 1958, Negishi did his internship at Teijin, where he conducted research on polymer chemistry.[9] Later, he continued his studies in the United States after having won a Fulbright Scholarship and obtained his Ph.D. from the University of Pennsylvania in 1963, under the supervision of professor Allan R. Day.[10][3]

Career

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Peter Diamond, Dale T. Mortensen, Christopher A. Pissarides, Konstantin Novoselov, Andre Geim, Akira Suzuki, Ei-ichi Negishi, and Richard Heck, Nobel Prize Laureates 2010, at a press conference at the Royal Swedish Academy of Sciences in Stockholm

After obtaining his Ph.D., Negishi decided to become an academic researcher.[11] Although he was hoping to work at a Japanese university, he could not find a position.[12] In 1966 he resigned from Teijin, and became a postdoctoral associate at Purdue University, working under future Nobel laureate Herbert C. Brown. From 1968 to 1972 he was an instructor at Purdue.[13]

In 1972, he became an assistant professor at Syracuse University, where began his lifelong study of transition metal–catalyzed reactions,[14] and was promoted to associate professor in 1979.[15] He returned to Purdue University as a full professor in the same year.[16]

He discovered Negishi coupling, a process which condenses organic zinc compounds and organic halides under a palladium or nickel catalyst to obtain a C-C bonded product. For this achievement, he was awarded the Nobel Prize in Chemistry in 2010.[17] Negishi also reported that organoaluminum compounds and organic zirconium compounds can be used for cross-coupling. He did not seek a patent for this coupling technology and explained his reasoning as follows: "If we did not obtain a patent, we thought that everyone could use our results easily."[18] In addition, Zr(C5H5)2 obtained by reducing zirconocene dichloride is also called Negishi reagent, which can be used in oxidative cyclisation reactions.[19][20] The technique he developed is estimated to be used in a quarter of all reactions in the pharmaceutical industry.[3]

By the time Negishi retired in 2019, he had published more than 400 academic papers.[3] He was committed to instilling rigorous practices in his lab, emphasizing the need of keeping organized and comprehensive records. Before any separations, he asked his student to evaluate crude reaction mixtures in order to minimize loss of any useful scientific information.[14]

Recognition

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From left: Suzuki, Negishi, and Heck (2010)

Awards

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  • 1996 – A. R. Day Award (ACS Philadelphia Section award)[21]
  • 1997 – Chemical Society of Japan Award[22]
  • 1998 – Herbert N. McCoy Award[22]
  • 1998 – American Chemical Society Award for Organometallic Chemistry[22]
  • 1998–2000 – Alexander von Humboldt Senior Researcher Award[22]
  • 2003 – Sigma Xi Award, Purdue University[22]
  • 2007 – Yamada–Koga Prize[23]
  • 2007 – Gold Medal of Charles University, Prague, Czech Republic[24]
  • 2010 – Nobel Prize in Chemistry
  • 2010 – ACS Award for Creative Work in Synthetic Organic Chemistry[23]
  • 2015 – Fray International Sustainability Award, SIPS 2015[25]

Honors

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Personal life and death

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Negishi began dating Sumire Suzuki in his freshman year and they announced their engagement to their parents in March 1958.[33] They had met at a choir of which they were both members at in university.[3] They married the next year and together they had two daughters.[34]

Negishi loved playing the piano and conducting. During the "Pacifichem" 2015 conference's closing ceremony, he conducted an orchestra.[14]

Disappearance

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On the evening of March 12, 2018, both Negishi and his wife were reported missing by family members. Police determined that, based on a purchase made earlier in the day, the couple had left their home in West Lafayette, Indiana, and headed north. At about 5 a.m. the next day, officers in Ogle County, Illinois, received a call to check on the welfare of an elderly man who was walking on a rural road south of Rockford. When he was taken to hospital, officers identified him as Negishi and found that police in Indiana were looking for him and his wife. A short time later, Suzuki's body was found at the Orchard Hills Landfill in Davis Junction, along with the couple's car.[34]

According to a statement from the family, the couple was driving to Rockford International Airport for a trip when their car became stuck in a ditch on a road near the landfill. Negishi went looking for help and was said to be suffering from an "acute state of confusion and shock". The Ogle County Sheriff Department said there was no suspicion of foul play in Suzuki's death, although the cause of her death was not immediately released. The family said Suzuki was near the end of her battle with Parkinson's disease.[34]

In May 2018, an autopsy concluded that Suzuki died from hypothermia, but Parkinson's disease and hypertension were contributing factors.[35]

Death

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Negishi died in Indianapolis, Indiana, on June 6, 2021.[3] He was 85 years old. No funeral services took place in the United States, but his family planned to lay him to rest in Japan in 2022.[21][36][37][8]

See also

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References

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  1. ^ "The Nobel Prize in Chemistry 2010".
  2. ^ Anthony O. King, Nobuhisa Okukado and Ei-ichi Negishi (1977). "Highly general stereo-, regio-, and chemo-selective synthesis of terminal and internal conjugated enynes by the Pd-catalysed reaction of alkynylzinc reagents with alkenyl halides". Journal of the Chemical Society, Chemical Communications (19): 683. doi:10.1039/C39770000683.
  3. ^ a b c d e f g h "Ei-ichi Negishi obituary". The Times. London. July 16, 2021. Retrieved January 16, 2021. (Subscription required.)
  4. ^ "Ei-ichi Negishi". Department of Chemistry Faculty Directory. Purdue University. Archived from the original on March 14, 2018. Retrieved March 26, 2018.
  5. ^ Press release, Great art in a test tube, Royal Swedish Academy of Sciences. Accessed October 6, 2010.
  6. ^ ノーベル化学賞に鈴木、根岸氏. 琉球新報. October 6, 2010. Archived from the original on November 30, 2010. Retrieved October 6, 2010.
  7. ^ （私の履歴書）根岸英一（2） 1年早く就学 8歳まで満州で生活 遊びに熱中、冬はスケート. The Nikkei. October 2, 2012. Retrieved August 30, 2015.
  8. ^ a b Chapman, Kit, Ei-ichi Negishi (1935–2021), Nature, July 1, 2021
  9. ^ BMBSC (November 27, 2019). "Ei-ichi Negishi". Birla. Archived from the original on June 21, 2021. Retrieved June 12, 2021.
  10. ^ "Penn Chemistry Alumnus wins Nobel Prize in Chemistry". www.chem.upenn.edu. Department of Chemistry, University of Pennsylvania. October 5, 2010. Retrieved June 12, 2021. Prof. Negishi received his Ph.D. from Penn Chemistry in 1963 under the supervision of Prof. Allan R. Day.
  11. ^ （私の履歴書）根岸英一（10） 帝人に復帰 大学で「優」連発、自信に 新製品阻まれ学会へ転進、日本経済新聞、2012年10月10日
  12. ^ ノーベル化学賞：根岸さんうっすら涙「来るものが来た」 Archived July 19, 2012, at archive.today、毎日新聞（電子版）、2010年10月7日
  13. ^ "Negishi Ei-ichi". Encyclopædia Britannica. April 24, 2017. Retrieved March 15, 2018.
  14. ^ a b c Ma, Shengming (July 23, 2021). "Ei-ichi Negishi (1935–2021)". Science. 373 (6553). AAAS: 400. Bibcode:2021Sci...373..400M. doi:10.1126/science.abk0608. ISSN 0036-8075. PMID 34437110.
  15. ^ "Ei-ichi Negishi, Nobel Prize Winner in Chemistry and Former Faculty Member, Dies at 85". SU News. June 25, 2021. Retrieved July 4, 2021.
  16. ^ "Syracuse University congratulates Ei-ichi Negishi on the 2010 Nobel Prize in chemistry". SU News. October 7, 2010. Retrieved July 22, 2020.
  17. ^ "ノーベル化学賞に鈴木名誉教授と根岸氏". Sankei Shimbun. October 6, 2010. Archived from the original on October 6, 2010. Retrieved October 6, 2010.
  18. ^ "根岸・鈴木氏、特許取得せず…栄誉の道開く一因". Yomiuri Shimbun. October 7, 2010. Archived from the original on October 9, 2010. Retrieved October 8, 2010.
  19. ^ Ilan, Marek (February 18, 2005). New Aspects of Zirconium Containing Organic Compounds. Springer Science & Business Media. pp. 138–. ISBN 978-3-540-22221-7.
  20. ^ Bloodworth, Sally (July 3, 2020). "Negishi's reagent". Chemistry World. Retrieved June 12, 2021.
  21. ^ a b Service, Purdue News. "Ei-ichi Negishi, one of 2 Nobel Prize winners from Purdue University, dies". www.purdue.edu.
  22. ^ a b c d e "Purdue University: Sigma XI: Faculty Research Awards 2003". www.purdue.edu.
  23. ^ a b c d e "National Academy of Sciences".
  24. ^ "2010 Nobel laureate to speak at University Feb. 1". January 25, 2012.
  25. ^ "Ei-ichi Negishi Winner of the Fray Award". www.flogen.org.
  26. ^ "Ei-ichi Negishi". Guggenheim Fellows. John Simon Guggenheim Memorial Foundation. Retrieved June 12, 2021. Fellow: Awarded 1986; Field of Study: Chemistry
  27. ^ "Professor Ei-ichi Negishi". J. Chem. Soc., Perkin Trans. 1 (9). Royal Society of Chemistry: 9–xii. 2001. doi:10.1039/b009326m.
  28. ^ "Negishi And Suzuki Awarded Japan's Order Of Culture". Chemical & Engineering News. Vol. 88, no. 48. American Chemical Society. November 29, 2010. Retrieved July 4, 2021.
  29. ^ "Purdue's Nobel laureate wins Japan's highest cultural honor". www.purdue.edu.
  30. ^ a b "Purdue's Nobel Laureate receives Order of the Griffin". www.purdue.edu.
  31. ^ "03/22/11, Penn's 2011 Honorary Degree Recipients and the 2011 Commencement Speaker – Almanac, Vol. 57, No. 26". almanac.upenn.edu.
  32. ^ "Japanese Nobel Prize Chemists Honored By Royal Society Of Chemistry". Asian Scientist Magazine. June 12, 2012.
  33. ^ "The Nobel Prize in Chemistry 2010". NobelPrize.org.
  34. ^ a b c Bangert, Dave (March 13, 2018). "Police: No foul play in death of wife of Purdue Nobel Prize winner found in Illinois". Journal and Courier. Retrieved July 22, 2020.
  35. ^ Wilkins, Ron. "Autopsy: Hypothermia, complicated by Parkinson's and hypertension killed professor's wife". Journal and Courier.
  36. ^ Chang, Kenneth (June 22, 2021). "Ei-ichi Negishi, Nobel Prize Winner in Chemistry, Dies at 85". The New York Times. Retrieved July 4, 2021.
  37. ^ NEWS, KYODO. "Japanese Nobel laureate chemist Negishi dies at 85". Kyodo News+.
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