Tamejiro Hiyama

Tamejiro Hiyama (born August 24, 1946 in Ibaraki , Osaka Prefecture) is a Japanese chemist. He is known for the Nozaki-Hiyama-Kishi reaction , a metal-catalyzed coupling reaction that has become of great importance for modern organometallic chemistry.

Career

Hiyama studied chemical engineering at the University of Kyoto with a bachelor's degree in 1969 and a master's degree in 1971. He was there then (from 1972) assistant to Hitoshi Nozaki and received his doctorate in Kyoto in 1975 and was a post-doctoral student at Harvard in 1975/76 University at Yoshito Kishi . From 1972 to 1981 he was associate professor at Kyoto University in the engineering faculty. At the same time he was group leader (from 1983 senior scientist) at the Sagami Chemical Research Center (SCRC) and most recently laboratory director from 1981 to 1992. In 1992 he became a professor at the Tokyo Institute of Technology at the Research Laboratory for Resource Use and from 1997 until his retirement in 2010 he was a professor at Kyoto University. Then he was a professor at Chuo University.

plant

He deals with organic synthesis (new organometallic reagents and reactions for targeted synthesis, synthesis of biologically active substances), organic fluorine compounds and organic silicon compounds.

The Nozaki-Hiyama-Kishi reaction is a cross-coupling reaction in which alcohols are formed from aldehydes and organic halogen compounds ( aromatics or those with an allyl group ) in the presence of chromium or nickel salts in an aqueous solution . Hiyama and Nozaki first reported this in 1977 with chrome. In a way, it was the chromium analogue of the magnesium-based Grignard reaction , but in contrast to this, it reacted very selectively with aldehydes and, unlike the Grignard reaction, tolerates a number of functional groups, which makes it more widely applicable. But there were problems with reproducibility. The group of Hiyama and Nozaki and the group of Yoshito Kishi , who was then working on the difficult synthesis of palytoxin and could well have used the reaction, finally found the cause in the need for small nickel impurities in the chromium. That is why the best (purest) chromium compounds delivered the worst results, but this could be corrected with only a few hundredths of a percent nickel added. The reaction is also used on an industrial scale.

He later researched cross -coupling reactions with organic silicon compounds , including in 1988 the Hiyama coupling , a reaction between organic silicon compounds and organic halogen compounds (with a whole range of possible functional groups) and a palladium catalyst.

${\displaystyle {\begin{matrix}{}\\{\ce {{R-SiR''_{3}}+R'-X->[\mathrm {F^{-}} ][{\text{Pd cat.}}]R-R'}}\end{matrix}}}$

• ${\displaystyle {\ce {R}}}$: 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 ( triflyl group )

In addition to over 400 scientific papers, he also published several books.

Honors and memberships

In 2012 he received a Humboldt Research Prize , in 2004 the Prize of the Japan Liquid Crystal Society (of which he was President from 2009 to 2011), in 2007 the Prize of the Society of Synthetic Organic Chemistry of Japan (of which he was Director 2003/04) and in 2008 the Prize the Chemical Society of Japan, whose prize for young chemists he had already received in 1980 and whose director he was from 1996 to 1998 and 2002. In 2011 he became chairman of the Japan Society for the Promotion of Science. He is a Fellow of the Royal Society of Chemistry.

From 2004 to 2012 he was editor of Chemistry Letters and 1994 to 1996 of the Bulletin of the Chemical Society of Japan.

Fonts (selection)

Except for the works cited in the footnotes.

• with K. Takai, K. Kimura, T. Kuroda, H. Nozaki: Selective grignard-type carbonyl addition of alkenyl halides mediated by chromium (II) chloride , Tetrahedron Letters, Volume 24, 1983, pp. 5281-5284
• with Y. Minami: Synthetic Transformations through Alkynoxy-Palladium Interactions and CH Activation , Acc. Chem. Res., Volume 49, 2016, pp. 67-77. * with T. Komiyama, Y. Minami: Recent Advances in Transition-Metal-Catalyzed Synthetic Transformations of Organosilicon Reagents , ACS Catal., Volume 7, 2017, pp. 631-651.

Books (selection):

• with Koichiro Oshima: Organic Synthetic Chemistry (Japanese), Tokyo Kagaku Dojin 2012
• with GS Zweifel, MH Nantz: Modern Organic Synthesis - An Introduction, Kagaku Dojin 2009
• with Kyoko Nozaki: Catalytic Reactions for Organic Synthetic Chemistry (Japanese), Tokyo Kagaku Dojin 2004
• Organofluorine Compounds: Chemistry and Applications , Springer, 2000, editor Hisashi Yamamoto.

literature

• Author Profile: Tamejiro Hiyama, Angewandte Chemie Int. Ed., Volume 56, 2017, Issue 9, pp. 2242–2244.

Web links

• Hiyama Lab , with biography / CV

Individual evidence

1. ↑ Y. Okude, S. Hirano, T. Hiyama, H. Nozaki: Grignard-type carbonyl addition of allyl halides by means of chromous salt. A chemospecific synthesis of homoallyl alcohols , J. Am. Chem. Soc., Vol. 99, 1977, pp. 3179-3181.
2. ↑ Derek Lowe, Das Chemiebuch, Librero 2017, p. 452
3. ↑ Hiyama, Y. Hatanaka: Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris (diethylamino) sulfonium difluorotrimethylsilicate , J. Org. Chem., Volume 53, 1988, pp. 918-920
4. ^ Hiyama, How I came across the silicon-based cross-coupling reaction , J. Organomet. Chem., Vol. 653, 2002, pp. 58-61