Reactive boron compounds having low oxidation state: boryl anion and diborane(4)
Makoto Yamashita
Department of Molecular&Macromolecular Chemistry, Graduate School of Engineering, Nagoya University
Abstract:
We recently synthesized boryllithium species which has a formal anionic charge and remarkable
nucleophilicity on its boron center. The latest development in chemistry of boryl anion, involving
deprotonation of H2 and benzene, will be presented.
On the other hand, we also reported synthesis of novel unsymmetrical diborane(4), pinB-BMes2, and its
reactivity towards CºO, CºN, and CºC triple bond. This interesting rectivity comes from its highly Lewis
acidic nature due to overlapping two vacant p-orbitals of pinB and BMes2 groups. Chemistry of Lewis acidic
diborane(4) will also be presented.
H2 (1 atm)
Dip N B N Dip
Li(thf)2
H
Dip N B N Dip
Li
K
Dip N B N Dip
Dip N B N Dip + LiH
H
> 95%
Dip N B N Dip
10 h, rt
Dip N B N Dip
H
cf. C6H6
pKa = 371)
H
Ph
Mes (1.1 equiv.)
pinB
BMes2 pinB
BMes2 Ph
BMes2
B B
w/wo additive
+
+
O
Mes
H
H
pinB
H
Ph
Ph
isomer a
isomer b
isomer c
diboration of alkyne without TM catalyst
O
Xyl
Xyl N C
N C Mes (1 equiv.)
B
O
O B Mes
ring contraction of Bpin
Mes
Mes
Xyl N C
C B
Mes (2 equiv.)
pinB N
C
B B
Xyl N
O
Mes
Xyl
O
References:
(1) Asakawa, H.; Lee, K.-H.; Lin, Z.; Yamashita, M., Nat. Commun. 2014, 5, 4245.
(2) Dettenrieder, N.; Aramaki, Y.; Wolf, B. M.; Maichle-Mössmer, C.; Zhao, X.; Yamashita, M.; No
zaki, K.; Anwander, R., Angew. Chem. Int. Ed. 2014, 53, 6259-6262.
(3) Asakawa, H.; Lee, K.-H.; Furukawa, K.; Lin, Z.; Yamashita, M., Chem. Eur. J. 2015, 21, 42674271.
(4) Asami, S.-s.; Okamoto, M.; Suzuki, K.; Yamashita, M., Angew. Chem. Int. Ed. 2016, 55, 1282712831.
(5) Katsuma, Y.; Asakawa, H.; Lee, K.-H.; Lin, Z.; Yamashita, M., Organometallics 2016, 35, 2563
-2566.
(6) Kisu, H.; Sakaino, H.; Ito, F.; Yamashita, M.; Nozaki, K., J. Am. Chem. Soc. 2016, 138, 35483552.
(7) Kojima, C.; Lee, K.-H.; Lin, Z.; Yamashita, M., J. Am. Chem. Soc. 2016, 138, 6662-6669.
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Makoto Yamashita
Affiliation: Department of Molecular&Macromolecular Chemistry, Graduate School of
Engineering, Nagoya University
Address: Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Phone: +81-52-789-3335
E-mail: [email protected]
Homepage: http://oec.chembio.nagoya-u.ac.jp/
Education
2002 Ph.D., Graduate School of Science, Hiroshima University (Prof. Yohsuke Yamamoto)
1997 BS, Faculty of Science, Hiroshima University (Prof. Kin-ya Akiba)
Professional Career
2016-present Professor, Nagoya University
2015-2016
Professor, Chuo University
2011-2015
Associate Professor (PI), Chuo University
2008-2011
Lecturer, The University of Tokyo (w. Prof. Kyoko Nozaki)
2007-2008
Assistant Professor, The University of Tokyo (w. Prof. Kyoko Nozaki)
2004-2007
Research Associate, The University of Tokyo (w. Prof. Kyoko Nozaki)
2003-2004
Postdoctoral Fellow, The University of Tokyo (w. Prof. Takayuki Kawashima)
2002-2003
Postdoctoral Fellow, Yale University (w. Prof. John F. Hartwig)
2008, 2013, 2015, 2017 Visiting Professor (Tokyo Tech, Rikkyo U, Kyoto U, U-Tokyo)
Awards and Honors
2015 Thieme Chemistry Journal Award 2015
2010 Banyu Chemist Award 2010
2009 The Young Scientists' Prize from the Minister of Education, Culture, Sports, Science
and Technology
2009 Chemical Society of Japan Award for Young Chemists
2005 Inoue Research Award for Young Scientist
Academic Activity
2016Chem. Soc. Rev., Advisory Board
2016Bull. Chem. Soc. Jpn., Associate Editor
2015-2017
Journal of Synthetic Organic Chemistry, Japan (SSOCJ), Editorial Board
2012-2014
Organometallics, International Advisory Board
Research Interest
Main Group Chemistry, Organometallic Chemistry, Homogeneous Catalysis, Industrial Chemistry
Hobbies
Chemistry, Beer with students and friends, Workout with heavy metal music (DragonForce, BABYMETAL)