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Top 5 Program (WPI) in Japan and Evaluation of Research
Accomplishments
International Chemical Conference、 Taipei, 2007 （ ICCT 2007)
Yoshinori Yamamoto
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan
The World Premier International Research Center (WPI) Project
The program provides priority support for projects aimed at creating top world-level research centers staffed at their
core with the world's most leading researchers.
“Global visibility"“Global visibility" that attracts top researchers from around the world
Number of WPI Centers
:
Period :
Expenditures :
Approximately 5
10 years, with possible 5-year extension for projects with outstanding results(An interim evaluation will be carried out five years after the project starts.)
Between 500 million yen and 2 billion yen annually per Center
· The WPI Research Center for Atom·Molecule·Materials (Tohoku University)
· Institute for the Physics & Mathematics of the Universe (The University of Tokyo)
· Institute for Integrated Cell-Material Sciences (Kyoto University)
· Osaka University Immunology Frontier Research Center (Osaka University)
· International Center for Materials Nanoarchitectonics (National Institute for Materials Science, Nims)
Selected WPI Projects
Objectives of the WPI Research Center
System Integrationthrough design and
evaluation
Device Developmentbased on a fundamentally
new approach
Development of New, Novel Compounds and Materials
Establish the Premier Research Center for MaterialsEstablish the Premier Research Center for Materials
Invent/develop New Innovative Functional Invent/develop New Innovative Functional MaterialsMaterials
TU WPITU WPIContributions to SocietyContributions to Society
Theory Computer Simulations
Process TechnologyProcessing Technique
CharacterizationEvaluation Analysis
Excellency in TU Research, Past, Present and Future with WPI
Past Achievements (Representative Examples) Novel development of devices for optical communication (J. Nishizawa)
Development of amorphous materials (T. Masumoto)Discovery of carbon nanotubes (S. Iijima, Ph.D.’65)Invention of new structural analysis of biopolymers (K. Tanaka, B.S. ‘83)
Recent AchievementsCreative development and practical applications of bulk metallic glasses (A. Inoue)
Current World-Prominent Researchers (based on citation analysis of ISI, July 2007) A. Inoue: 1st place in Material Science T. Takahashi: 19th place in Physics Y. Yamamoto: 17th place in Chemistry
Material Science: Physics : Chemistry :
Current World Ranking of Tohoku University(based on citation analysis of ISI, July 2007)
3rd place9th place18th place
Invention of Substances & Materials
Characterization
Theory &Simulation
Device Development
System Integration
Atom.Molecule (Phys, Chem) Materials Engineering
Inoue, Chen, ItayaKawasaki, Tanigaki, Nishi,Yamaguchi, Shimomura, Greer, Yavari
Takahashi, Yamada, NishiHashizume, Itaya,
Tokuyama,Tsukada,Shluger
Inoue, Chen,Kawasaki, Tanigaki,Adschiri, Shimomura, Lagally, Hemker
Takahashi,Yamada,Hashizume,Ikuhara,Weiss, Xue
Tokuyama,Tsukada,Shluger, Wan
Miyazaki, Tromp, Nakazawa, OhmiRussell, Shimomura
Ohmi, Nakazawa,Gessner
Esashi, Ohmi,Gessner
Ohmi, Esashi,Nakazawa,Greer
How Can We Achieve the Objectives? Outline of Research Fields & Fusion
Inoue,Kawasaki, Adschiri,Shimomura,Lagally, Hemker
Itaya,Ikuhara,Weiss,Xue
Shluger, Wan
Xue, Tromp, Lagally, Hashizume
Tromp, Nishi, Esashi
North America
Europe
Overseas Footholds of Tohoku Overseas Footholds of Tohoku University around the WorldUniversity around the World
Asia・
Oceania
through global cooperationTohoku University WPITotal number about 200 (2007)
WPI researcher groups encompass many regions of the
world (2017)
Overseas Network
Tohoku Tohoku University University
WPIWPI• Tohoku University US Office (California)• University of California (SB)• MIT• Harvard University• Stanford University• Columbia University• University of Illinois• University of Wisconsin• University of Iowa • Argonne Natl. Lab.• IBM Watson and Almaden• Johns Hopkins University• Penn State University
• University of Cambridge• Royal Institute of Technology in Stockholm• University of Lyon• Russian Academy of Sciences• University of Oxford• University of Heidelberg• Moscow State University• ETH• IBM Zurich
• Tohoku University China Office (Beijing)• Indian Institute of Science• Seoul National University• Korea Advanced Institute of Science and Technology• Chinese Academy of Sciences• Tsinghua University• University of New South Wales• University of Sydney
Current: Equal reward, equal space, equal treatments based on traditional promotion system, with the exception of some competitive grants
Drastic Departure
from Traditional Japanese Equalitarianism
TU
WP
IT
U W
PI
New System and Research Environment of WPI
Evaluation/Promotion based on Performance and Future Potential
Fair Merit System instead of Equalitarianism
Search/Secure Gifted Young Talents andEncourage/Support “Blue-Sky” Research
WPI Research Center for Atom·Molecule·Materials
PI; 30 people (11 from US, UK, Germany, France, and China)
Researchers; 90 people (associate & assistant professors, postdoctoral fellow; “~30 % “should be from abroad)
Technicians and Officers; 90 people
WPI-AIMR started on October 1, 2007
One of the Selection Criteria for PI; Citation Analysis
• Citation of Y. Yamamoto (on December 4, 2007)
• Number of Papers found: 596, Sum of the Times Cited: 17174
• Average Citations per Item: 28.82, h-index: 58
Only the first 20 years are displayed. Only the first 20 years are displayed.
ISI (Thomson, 2006) vs. Scopus (Elsevier, 2007); Ranking of Universities, based on
Times Higher Education Supplement (THES)1 (1). Harvard2 (2). Cambridge, Oxford, Yale.....17 (19). The University of Tokyo…..25 (29). Kyoto University…..46 (70). Osaka University…..102 (108). National Taiwan University…..102 (168). Tohoku University
Scopus covers journals written in languages other than English.
Most Cited 10 Papers in Tetrahedron Letters during 1996-2007
Grubbs, R. H…. RCM activities of Ru-based olefin metathesis catalysts, TL, 1999, 40, 2247, 488
Frustner, A……Ru carbene complexes…….by RCM, TL, 1999, 40, 4787, 255
Miyano, S…..Synthesis of p-tert-butylthiacalix[4]arene…., TL, 1997, 38, 3971, 251
Lygo, B……Asymmetric phase transfer catalysts derived from Cinchona alkaloids…., TL,
1997, 38, 8595, 223
Chan, D. M.T…..New N- and O-arylation with PhB(OH)2 and Cupric Acetate, TL, 1998, 39, 2933, 207
Obika, S…….Duplexes containing nucleosides analogues…TL, 1998, 39, 5401, 204
Nishiyama, M…..N-Arylpiperidines from aryl halides and piperidine under Pd tri-t-butylphosphine catalyst, TL, 1998, 39, 617, 201
Nishiyama, M…..Pd-catalysed synthesis of triarylamines from aryl halides and diarylamines, TL, 1998, 39, 2367, 198
Kalder, S. W…..Solid-supported nucleophiles and electrophiles for the purification of non-peptide small molecules, TL, 1996, 37, 7193, 196
Welton, T…..Diels-Alder reactions in room temperature ionic liquids, TL, 1999, 40, 793, 186
Most Cited 10 Papers in Tetrahedron during 1996-2007
Grubbs, R. H…. Recent advances in olefin metathesis, T, 1998, 54, 4413, 1694
Lindstrom, P…..Microwave assisted organic synthesis, T, 2001, 57, 9225, 1027
Basavaiah, D…..The Baylis-Hillman reaction….T, 1996, 52, 8001, 598
Loupy, A…..A tentative rationalization of microwave effects in organic synthesis, T, 2001, 57, 9199, 576
Stanforth, S. P. Catalytic cross-coupling reactions in biaryl synthesis, T, 1998, 54, 263, 568
Hermkenns, P. H. H…..Solid-phase organic reactions, T, 1996, 52, 4527, 501
Hanessian, S…..Conformationally constrained amino acids as versatile scaffolds….T, 1997, 53, 12789, 455
List, B……Proline-catalyzed asymmetric reactions, T, 2002, 58, 5573, 409
Chan, T.-H…..Indium mediated and catalyzed reactions in aqueous media, T, 1999, 55, 11149, 409
Kotha, S…..Recent applications of the Suzuki-Miyaura cross-coupling….., T, 2002, 58, 9633, 407
Elsevier Journals Downloaded Frequently
USA 24.68%
UK 9.59%
Japan 7.14%
France 5.33%
Korea 5.19%
China 3.78%
Canada 3.41%
Australia 3.34%
Brazil 2.90%
Germany 2.84%
The Lancet 1.56%
Tetrahedron Letters 1.55%
Cell 0.99%
Biochemical and Biophysical Research Communications
0.97%
Tetrahedron 0.93%
FEBS Letters 0.87%
Journal of Chromatography A 0.67%
Journal of Molecular Biology 0.60%
Journal of the American College of Cardiology
0.58%
Brain Research 0.55%
Countries
Data in 2006
From - to -Electrophilic Lewis Acids. Application to Selective
Organic Transformations
Yoshinori Yamamoto
Department of Chemistry, Graduate School of Science, Tohoku University,
Sendai, Japan
-Electrophilic Lewis Acids
-Electrophilic Lewis Acids
LA
LALA
LA
-binding
LA = PtCl2, CuCl, AuCl, etc.
X XLA
LA
-binding
LA = AlCl3, BCl3, etc. X = O, N
O
H
1
BCl3 MgCl2 CuCl CuCl2 AuCl AuCl3 PtCl2
18.9 34.5 37.4 25.4 33.1 35.9 46.9
LA + SH
LA S
S = Benzaldehyde
LA
H
25
30
35
40
45
50
H, kcal/mol
AnionBr Cl F OTf BF4 SbF 6PF6
Pt
Au
Cu
Ag
21.0
46.7
2.3
2.9 1.6
1.8
2.9
1.0 1.5
1.1 1.9
1.1 1.0 1.4
H1/H3
H2/H3
O
H
1
NH
H
2 3
BCl3 MgCl2 CuCl CuCl2 AuCl AuCl3 PtCl2 LA
0.8
1.0
1.2
1.4
1.6
1.8
AnionBr Cl F OTf BF4 SbF 6PF6
Pt
Au
Pt
Au
Cu
Cu
Ag
Ag
H2/H3
H1/H3
Allylation-RCM Strategy
-Electrophilic Lewis Acids
O
O
Bu3Sn
OR
O
OLA
-
+H H
H H
R = COCH2Cl
allylation
LA
O
O
O
O
H H H
H H H
O
O
O
O
H H H
H H H
RCM
X XLA
LA
-binding
LA = AlCl3, BCl3, etc. X = O, N
O
O
O
O
O
O
O
O
O
OO
MeH
MeH Me
MeH H
H
Me
HOCHO
H
H
HMe
HHHH
Me
HH
O
HA
BC
D F
H
I
K
O
O
O
O
O
O
O
MeH Me H H
Me Me H
MeHHH
MeHHH
OH
A B C D
F
O
O
OTBSMeH
H H
HO2C
TESO
K
O
O
O
OPh
H Me
H H H
HOTBS
B C
O
O
Me Me H
MeHH
OBn
F
OBnHO
Total Synthesis of Brevetoxin B
Retrosynthetic Analysis
OTBDPS
E
G
J
E G J+
+ G
Brevetoxin B
Me
SPh
Cl
K. Nakanishi, et al.J . Am. Chem. Soc. 1981, 103, 6773.
O
O
O
Ph
H Me
HHO
O
H
H
O
Me
O
O
OBnMe Me H
H H Me
Bu3Sn
SPh
O
O
O
O
O
O
O
O
H Me H HMe Me H
MeHHH
MeHHH
OBn
Ph
O
O
OH HMe Me
HHH
MeH
O
O
O
O
O
O
O
O
H H H Me
Hb H H Me
H Me H HaMe Me H
OBn
Ph
B C D
F
OBn
OBn
OBn
PCy3
Ru
PCy3
Cl
Cl
Ph
AgOTf, MS4ACH2Cl2, -78 °C to rt
+
E G
72%
78 : 22
76%
Synthesis of the ABCDEFG Ring Segment (3)
JHa-Hb = 9.2 Hx
NOE
O
O
O
O
O
O
H H H Me
H H H Me
H Me H HMe Me H
O
O
Me O
O
OTBS
H H
H Me
OTBDPSO
SnBu3
OR
R = COCH2Cl
O
O
O
O
O
O
O
O
O
O
O
Me
HH
H
MeH H
HMe
HH
H
HMe
H H MeMe
H H
H
Me
TBSO OTBDPS
Intramolecular Allylation
A B C DE F G J K
AB
CD E
FG
JK
I
Lewis acid
O
O
MeH
H
H H
H
G
JI+
Lewis acid
MgBr2·OEt2
MgBr2·OEt2
BF3·OEt2
solvent
CH2Cl2
CH3CN
CH3CN
temp
0 °C
40 °C
-40 °C to rt
yield (ratio)
78% (50 : 50)
82% (>99 : 1)
33% (>99 : 1)
Kadota, I.; Takamura, H.; Nishii, H.; Yamamoto, Y. J. Am. Chem. Soc. 2005, 127, 9246
O
O
O
O
O
O
O
O
O
OO
MeH
MeH Me
MeH H
HMe
HOCHO
HH
HMe
HHHH
Me
HH
H
O
Brevetoxin B
1H NMR Spectra (400 MHz, CDCl3) of Brevetoxin B
Synthetic
Natural
-Electrophilic Lewis Acids
Asao, N.; Takahashi, K.; Lee, S.; Kasahara, T.; Yamamoto, Y. JACS, 2002, 124, 12650
R RO
O
H+
cat. AuCl3
R RO
O
H+
cat. AuCl3
LA
LALA
LA
-binding
LA = PtCl2, CuCl, AuCl, etc.
CHO
RAuCl3
RCl3Au
O
O
AuCl3
R
R1
R2
O
AuCl3
AuCl3
R1
O R
R2
R2 R1R
RO
R1
R2
O
AuCl3
R
R1
R2
CHO
RAuCl3
RCl3Au
O
O
AuCl3
R
R1
R2
O
AuCl3
AuCl3
R1
O R
R2
R2 R1R
RO
R1
R2
O
AuCl3
R
R1
R2
Total Synthesis of (+)-Ochromycinone via Gold-CatalyzedIntramolecular [4 + 2] Benzannulation
Helicobacter pylori
R1 = Me, R2 = R3 = H, R4 = OH
(+)-Ochromycinone
Selective activity against H. pylor i 2)
OO
R4 O
R1
R2
R3
Angucyclinone Group 1)
H. Pylori is infested in half man's stomach of about
all population and is considered as a leading cause
of gastric ulcer and cancer.
B. J. Marshall and J. B. Warren won Nobel pr ize
in 2005 by distinguished achievement that had
discovered H. Pylor i.
2) Taniguchi, M.; Nagai, K., Watanabe, M.; Niimura, N.; Suzuki, K.; Tanaka, A. J. Antibiot. 2002, 55, 30-35.1) Carreno, M. C.; Urbano, A. Synlett 2005, 1, 1-25.~
Synthesis of Intramolecular Benzannulation Precursor
CHO
MeO
OMeMeO
TMS
trans/cis = 95/5
O
OMeO
Br
O
OMeO
BrMeO
OMeMeO
Br
MeO
OMeMeO
BrMeO
OMeMeO
Br
CHO
CO2HAgNO3
(NH4)2S2O8
65 %
SnCl2, conc HCl
then Me2SO4 50 % aq KOH
97 %
92 %
KOtBu O3, PPh3
79 %
Pd2(dba)3P(tBu)3
CHCl3
97 %
diyne segment
TBAF, AcOH
quant CHO
MeO
OMeMeO
CHO
MeO
OMeMeO
MeO
OMe
O
MeO
2 mol % AuCl3
50 °C, 1 h
84 %+ M - M
O
O
O
MeO97 % 84 %
BCl3
{[19D + 79.6 (c 0.5, CHCl3)}
O
O
O
{[20D + 98.4 (c 0.08, CHCl3), 99 % ee}
(+)-Rubiginone B2 (+)-Ochromycinone
CAN
HO
Total Synthesis of (+)-Ochromycinone
O M
MeO
MeO
MeO
MeO
OMeMeO
O
M
Application of Polycyclic Aromatic Hydrocarbons (PAHs )
n
RO
R
F. A. Cotton J. Am. Chem. Soc. 2001, 123, 11655-11663.
H. U. Bryant U.S.1999, 5889000
electrical conductors photosensitive devices
pharmaceutical agent
Organic conductorOrganic solar battery
Synthesis of Chrysene
CHO
Ph
+
Ph
(CH2Cl)2, HCF2COOH, 100oC
10 mol% Cu(OTf)2
Ph71%
CHO
Ph
+
Ph
(CH2Cl)2, HCF2COOH, 100oC
10 mol% Cu(OTf)2
Ph68%
CHO
Ph
H+
CuPhPh Ph
+cat. Cu(OTf)2
Synthetic Plan
R1 R1
10 mol% Cu(OTf)2
Ph
Phtoluene, 0.5 eq H2O, 100oC
R2 R2
R1 R2
Me
Ph
tBu
Ph
H
H
H
Me
91%
yield
>99%
94%
>99%
CHO
R
+
X
Synthesis of Anthracene
CHO
Ph
+
I
MePh
10 mol% Cu(OTf)2
(CH2Cl)2, 80oC
HCF2COOH
I
MePh
49%
MePh
Ph
85%
10 mol% Cu(OTf)2
tol, H2O, 100oC
Ph
MePh
quant.
(PPh3)2PdCl2CuI, Et3N
Ph
3 steps 42%
Acknowledgment
Computations; Associate Professor Ilya Gridnev
Polycyclic Ether Natural Product Synthesis (-Electrophilic Lewis Acids); Associate Professor I. Kadota; Dr. H. Takamura;
Dr. A. Ohno; Dr. C. Kadowaki; Dr. C. Park; Dr. S. Torand; Dr. P. Chan; Ms. M. Kawada; Ms. S. Saya; Ms. N. Oguro; Ms. K. Sato, Ms. K. Matsuda;
Mr. H. Ueno; Mr. H. Nishii; Mr. T. Abe; Mr. S. Kikuchi; Mr. Y. Sato
Coinage Metal Catalyzed Reactions (-Electrophilic Lewis Acids); Associate Professor N. Asao; Assistant Professor T. Jin;
Dr. T. Nogami; Dr. S. Lee; Dr. S. Yudha; Dr. K. Sato; Ms. K. Takahashi; Mr. T. Kasahara; Mr. H. Aikawa; Mr. Menggenbateer; Ms. Y. Isogai
\; MEXT (Ministry of Education, Science, Culture, Sports, Science and Technology)
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