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Tamejiro Hiyama (born August 24, 1946) is a Japanese organic chemist. He is best known for his work in developing the Nozaki-Hiyama-Kishi reaction and the Hiyama coupling. He is currently a professor at the Chuo University Research and Development Initiative, and a Professor Emeritus of Kyoto University.

Career

Hiyama received his Bachelor of Engineering (1969) and Master of Engineering (1971) from Kyoto University. He dropped out of the doctorate track in 1972, and subsequently started working as an assistant for Hitoshi Nozaki at Kyoto University. In 1975, he obtained his doctoral degree, and during 1975-1976 conducted postdoctoral research with Yoshito Kishi at Harvard University. In 1981, he started working at the Sagami Chemical Research Center, and became a principal investigator in 1983, and then chief laboratory manager in 1988.

In 1992, he re-entered the world of academia at the Tokyo Institute of Technology as a professor of the Research Laboratory of Resources Utilization. He then returned to Kyoto University in 1997 as a professor of engineering, until 2010 when he transferred to Chuo University, where he currently holds tenure.

His current research focuses on C-H activation and cross-coupling reactions. In particular, he is interested in ortho and benzylic C-H activation, and C-C, C-N, and C-Si bond formation via cross-coupling with organosilicon reagents.

In his spare time, he enjoys listening to classical music. His favorite way of spending a holiday is “cleaning small garden by picking out weeds one by one”, which is “good psychological training for a Buddhist priest”.

Major contributions

Hiyama is best known for developing:

• The Nozaki-Hiyama-Kishi reaction (NHK reaction) is a nickel/chromium mediated cross-coupling reaction between an allyl, vinyl or aryl halide and an aldehyde to form an alcohol upon aqueous workup.

It was originally discovered in 1977, where Hiyama and Nozaki reported a chemospecific synthesis of homoallyl alcohols from an aldehyde and allyl halide using chromium(II) chloride. In 1983, Hiyama and Nozaki published another paper extending the scope of the reaction to include aryl and vinyl halides. In 1986, Nozaki and Kishi independently discovered that the reaction depended on the nickel impurities in the chromium(II) chloride salt. Since then, nickel(II) chloride has been used as a co-catalyst.

The NHK reaction demonstrates high chemoselectivity towards aldehydes, as it tolerates a range of functional groups, and has been used on the process scale.

• The Hiyama coupling is a palladium-catalyzed cross-coupling reaction between aryl, alkenyl or alkyl halides and an organosilicon compound to form a C-C bond.

${\displaystyle {\begin{matrix}{}{\ce {{R-SiR''_{3}}+R'-X->R-R'}}\end{matrix}}}$

• ${\displaystyle {\ce {R}}}$: Aryl, Alkenyl or Alkynyl
• ${\displaystyle {\ce {R'}}}$: Aryl, Alkenyl, Alkynyl or Alkyl
• ${\displaystyle {\ce {R''}}}$: Cl, F or Alkyl
• ${\displaystyle {\ce {X}}}$: Cl, Br, I or OTf

Hiyama developed this reaction in 1988. He says he developed this method in order to overcome the shortcomings of Grignard reagents. While Grignard reagents are powerful, Hiyama says, they can be hard to use in total synthesis as they are not as tolerant of other functional groups.

Publications

He has published over 400 papers and 25 books over the course of his career.

Notable publications include:

• Tamejiro Hiyama and Koichiro Oshima, “有機合成化学” , Tokyo Kagaku Dojin, 2012, ISBN 978-4807907601
• G. S. Zweifel, M. H. Nantz, Tamejiro Hiyama, “最新有機合成法　設計と戦略 – Modern Organic Synthesis: An Introduction”, Kagaku Dojin, 2009, ISBN 978-4759811742
• Tamejiro Hiyama, coedited by Kyoko Nozaki, “有機合成のための触媒反応103” , Tokyo Kagaku Dojin, 2004, ISBN 978-4807905867
• Tamejiro Hiyama, “Organofluorine Compounds: Chemistry and Applications”, Springer, 2000, ISBN 978-3-662-04164-2
• Tamejiro Hiyama, coedited with Martin Oestreich, “Organosilicon Chemistry: Novel Approaches and Reactions”, Wiley-VCH, 2019, ISBN 978-3-527-34453-6
• Tamejiro Hiyama, coedited by Kyoko Nozaki, Yoshiaki Nakao, and Koji Nakano, “有機合成のための新触媒反応101” , Tokyo Kagaku Dojin, 20021, ISBN 978-4-8079-2005-1

See also

• Nozaki-Hiyama-Kishi reaction
• Hiyama coupling
• Oxidative Desulfurization Fluorination
• Carbostannylation of Alkynes and Alkenes
• Carbocyanation of Alkynes and Alkenes

References

1. Hiyama Lab Website--About Hiyama Archived May 3, 2017, at the Wayback Machine
2. Minami, Y.; Hiyama, T. (2016). "Synthetic Transformations through Alkynoxy-Palladium Interactions and C-H Activation". Acc. Chem. Res. 49 (1): 67–77. doi:10.1021/acs.accounts.5b00414. PMID 26651014.
3. Komiyama, T.; Minami, Y.; Hiyama, T. (2017). "Recent Advances in Transition-Metal-Catalyzed Synthetic Transformations of Organosilicon Reagents". ACS Catal. 7 (1): 631–651. doi:10.1021/acscatal.6b02374.
4. Hiyama Lab Website--Research Archived February 23, 2017, at the Wayback Machine
5. ^ Hiyama Interview
6. Hiyama, T. (2017). "Author Profile: Tamejiro Hiyama". Angew. Chem. Int. Ed. 56 (9): 2242–2244. doi:10.1002/anie.201608230.
7. Okude, Y.; Hirano, S.; Hiyama, T.; Nozaki, H. (1977). "Grignard-type carbonyl addition of allyl halides by means of chromous salt. A chemospecific synthesis of homoallyl alcohols". J. Am. Chem. Soc. 99 (9): 3179–3181. doi:10.1021/ja00451a061.
8. Takai, K.; Kimura, K.; Kuroda, T.; Hiyama, T.; Nozaki, H. (1983). "Selective grignard-type carbonyl addition of alkenyl halides mediated by chromium(II) chloride". Tetrahedron Letters. 24 (47): 5281–5284. doi:10.1016/S0040-4039(00)88417-8.
9. Takai, K.; Tagashira, M.; Kuroda, T.; Oshima, K.; Utimoto, K.; Nozaki, H. (1986). "Reactions of alkenylchromium reagents prepared from alkenyl trifluoromethanesulfonates (triflates) with chromium(II) chloride under nickel catalysis". J. Am. Chem. Soc. 108 (19): 6048–6050. doi:10.1021/ja00279a068. PMID 22175376.
10. Haolun, J.; Uenishi, J.; Christ, W.J.; Kishi, Y. (1986). "Catalytic effect of nickel(II) chloride and palladium(II) acetate on chromium(II)-mediated coupling reaction of iodo olefins with aldehydes". J. Am. Chem. Soc. 108 (18): 5644–5646. doi:10.1021/ja00278a057.
11. Thomé, I.; Nijs, A.; Bolm, C. (2012). "Trace metal impurities in catalysis". Chem. Soc. Rev. 41 (3): 979–987. doi:10.1039/c2cs15249e. PMID 22218700.
12. Hodgson, David M. (1994). "Chromium(II)-based methods for carbon-carbon bond formation". J. Organomet. Chem. 476 (1): 1–5. doi:10.1016/0022-328X(94)84132-2.
13. Chase, Charles; Austad, Brian; Benayoud, Farid; Calkins, Trevor; Campagna, Silvio; Choi, Hyeong-Wook; Christ, William; Costanzo, Robert; Cutter, James; Endo, Atsushi; Fang, Francis; Hu, Yongbo; Lewis, Bryan; Lewis, Michael; McKenna, Shawn; Noland, Thomas; Orr, John; Pesant, Marc; Schnaderbeck, Matthew; Wilkie, Gordon; Abe, Taichi; Asai, Naoki; Asai, Yumi; Kayano, Akio; Kimoto, Yuichi; Komatsu, Yuki; Kubota, Manabu; Kuroda, Hirofumi; Mizuno, Masanori; et al. (2013). "Process Development of Halaven®: Synthesis of the C14-C35 Fragment via Iterative Nozaki-Hiyama-Kishi Reaction-Williamson Ether Cyclization". Synlett. 24 (3): 327–332. doi:10.1055/s-0032-1317920.
14. Hatanaka, Y.; Hiyama, T. (1988). "Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino) sulfonium difluorotrimethylsilicate". J. Org. Chem. 53 (4): 918–920. doi:10.1021/jo00239a056.
15. Hiyama, T. (2002). "How I came across the silicon-based cross-coupling reaction". J. Organomet. Chem. 653 (1–2): 58–61. doi:10.1016/S0022-328X(02)01157-9.
16. Hiyama Lab Website-Publications Archived April 21, 2017, at the Wayback Machine

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External links

• Hiyama Lab Website

• 1946 births
• Living people
• Japanese organic chemists
• Foreign members of the Royal Society