Transcript Catalytic Reactions Involving Activation of Unreactive Bonds

Department of Chemistry
Seminar Announcement
Date/Time/Venue
Title/Speaker
26 Jan (Wed)
4pm – 5pm
Catalytic Reactions Involving Activation
of Unreactive Bonds
@ S8 Level 3
Executive
Classroom
Professor Naoto Chatani
Osaka University , Japan
Host : Asst Prof Martin J Lear
About the Speaker
Professor Naoto Chatani studied chemistry at Osaka University and
received his Ph. D. in 1984 under the guidance by Professors Noboru
Sonoda and Shinji Murai. In 1984 he joined the Institute of Scientific
and Industrial Research at Osaka University and worked in the
laboratory of Prof. Terukiyo Hanafusa. After postdoctoral studies
(1988-1989 under Prof. Scott E. Denmark, the University of Illinois,
Urbana-Champaign), he moved back to Osaka University and
worked with Prof. Shinji Murai as Assistant Professor. He was
promoted to Associate Professor in 1992 and Professor in 2003. He
received Young Chemist Award of the Chemical Society of Japan in
1991 and The fourth Green and Sustainable Chemistry Award: Minister of Education,
Sports, Culture, Science and Technology Prize in 2005. His current research interests
center on the area of catalysis.
Abstract
We reported some results for a series of Ru- and Rh-catalyzed carbonylation reactions of C-H bonds. In
all cases, the substrates required the presence of an sp2 nitrogen. This suggests that the coordination of
the sp2 nitrogen to the catalyst is an important for the reaction to proceed. Our findings also showed that,
in such carbonylation reactions of C-H bonds, both high CO pressures and high reaction temperatures
were required for a successful reaction. Because of this, carbonyl compounds, such as ketones, esters,
and amides are not typically used in the Ru- and Rh-catalyzed C-H bond carbonylation because of their
low coordination ability. The substrates must compete with the higher pressure of CO. This encouraged
us to develop a new bidentate system that would be applicable to the ortho C-H bond carbonylation of
aromatic amides.[1]
N
H
+
N
H
O
5 mol% Ru3(CO)12
H2O (2 equiv)
ethylene (7 atm)
O
CO
10 atm
N
toluene, 160 °C, 24 h
O
N
77%
We found new types of some catalytic reactions involving the cleavage of C-CN bonds in nitriles, which
proceed via a silicon-assisted mechanism.[2] Silylation,[3] reductive decyanation,[4] intramolecular C-C
bond formation,[5] and the Mizoroki-Heck type reaction[6] will be discussed.
Rh Si
R
C N
Si
R
C
R
N
CNSi
Rh
Rh
Si
Si
SiEt3
H Si
R Si
R H
R
Ar
R
SiEt3
Inoue, S.; Shiota, H.; Fukumoto, Y. Chatani, N. J. Am. Chem. Soc. 2009, 131, 6898.
Taw, F. L.; Mueller, A. H.; Bergman, R. G.; Brookhart, M. J. Am. Chem. Soc. 2003, 125, 9808.
[3] Tobisu, M.; Kita, Y.; Chatani, N. J. Am. Chem. Soc. 2006, 128, 8152.
[4] Tobisu, M.; Nakamura, R.; Kita, Y.; Chatani, N. J. Am. Chem. Soc. 2009, 131, 3174.
[5] Tobisu, M.; Kita,Y.; Ano, Y.; Chatani, N. J. Am. Chem. Soc. 2008, 130, 15982.
[6] Kita, Y.; Tobisu, M. ; Chatani, N. Org. Lett. 2010, 12, 1864.
[1]
[2]
All are Welcome