Title Studies on Catalytic Transformation of Aldehydes via η^2-Coordination to Nickel(0)

109 Pages·2012·9.31 MB·English

Studies on Catalytic Transformation of
Title
Aldehydes via η^2-Coordination to Nickel(0)
Author(s) Hoshimoto, Yoichi
Citation
Issue Date
oaire:version VoR
URL https://hdl.handle.net/11094/27542
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Doctoral Dissertation
of
Studies on Catalytic Transformation
Aldehydes viaゲロCoordination to Nickel(0)
Yoichi Hoshil■oto
January 2013
Graduate School of Engineering
Osaka University
Doctoral Dissertation
Studies on Catalytic Transformation of
Aldehydes viaゲ ‐C00rdination tO Nickel(0)
Yoichi Hoshilnoto
January 2013
Graduate School of Engineering
Osaka University
Preface and Acknowledgements
The study in this thesis has been carried out under the direction of Professor Sensuke
Ogoshi at the Department of Applied Chemistry Faculty of Engineering, Osaka
University from April 2003 to March 2013. The thesis describes the catalytic
transformation of aldehydes via r1'-cootdination to nickel(0).
For accomplishment of my works, there were really lots of helps, advices, and
supports. I owe all of them a great debt of gratitude; however, I regret to say that I
cannot all ofthem here.
I wish to express my greatest gratitude to Professor Sensuke Ogoshi (BOSS) for a
great number of suggestions, discussions, and encouragements (he often said to me
iOgftnut!").
He was really strict about chemistry and always gave me logical
directions. In addition, his enthusiasm for chemistry always filled me with a feeling of
respect.
I would like to express my appreciation to Professor Nobuaki Kambe and Professor
Naoto Chatani for their stimulating discussions.
I would like to give my special thanks to Professor Tetsuro Murahashi at Institute for
Molecular Science and Assistant Professor Masato Ohashi for their valuable and
productive advices. They taught me an importance of perseverance.
I deeply thank Ms. Noriko Fujimoto for her everyday lovely smile, and
heart-warming encouragements.
My especially thanks go as well to the past and present members in the Ogoshi Group.
When I joined the group in April 2007 as a bachelor student, many talented seniors, Dr.
Yasuki Tatsumi (a tenible but respectful drinker), Mr. Katsunori Shirato, Mr. Yoshinori
Ohe, Mr. Masahiro Ikawa (he always encouraged me), Mr. Ryo Inoue, Dr. Takashi
Tamaki (very respectful senior in my Ph.D student course), gave me lots of advices
about experimental know-how. As colleagues for the master's course, Mr. Osamu
Kishizaki, Mr. Koji Chiyoda, Mr. Toshifumi Haba, and Ms. Adusa Fukushima always
helped my laboratory's life.
I am much obliged to all of my juniors in the Ogoshi Group, Mr. Tadashi Kambar4
Mr. Tomoaki Taniguchi, Mr. AkiraNishimura, Mr. Kentaro Usui, Mr. Hiroki Saijyo, Mr.
Ippei Takeda, Mr. Kohe Takase, Ms. Haruka Suzuki (she worked with me for 3 years,
and showed me a lot of surprising and intriguing results), Mr. Ryohei Doi, Mr. Ryohei
Kamura, Mr. Yuki Tachibana, Mr. Hiromu Tokura, Mr. Tomoya Ohata, Mr. Seita Kimura,
Mr. Mitsutoshi Shibata, Ms. Yukari Hayashi (she worked quite hard and helped me for 2
years), Mr. Hiroaki Saito, Mr. Hironobu Sakaguchi, Ms. Eri Tamai, and Mr. Hayato
Yabuki (he worked with me since September 2012, and studied vigorously) for their
kind dedications.
I would like to thank Dr. Nobuko Kanehisa for her helpful assistance for X-ray
crystallographic analysis. Thanks are also due to the Instrumental Analysis Center,
Graduate School of Engineering, Osaka University, for the measurement of spectral and
analytical data.
I acknowledge the Research Fellowship from the Japan Society for the Promotion of
Science for Young Scientists (April 2010-May 2013) and the Global COE Program
"Global Education and Research Center for Bio-Environmetal Chemistrv" of Osaka
University.
Finally, my utmost gratitude is dedicated to my mother, Mr. Hatsuko Hoshimoto, and
all of my relatives in Nagano, for their understanding and encouragements.
January 2013
Yoichi Hoshiinoto
Contents
I
Chapter
General Introduction
Chapter 2
Ni(O)-Catalyzed lntramolecular Hydroacylation via 9
ry2-Rldehyde)( 72-Alkene)Nickel(0) Intermediate
1
Chapter 3
of Aldehydes via
Ni(0)-catalyzed Homo-Dimeization 39
nis( ry2-Aldehyde)Nickel(0) Intermediate
Chapter 4
Ni(0)-Catalyzed Crossed Tishchenko Reaction of Aliphatic Aldehydes with 53
Aromatic Aldehydes
Chapter 5
Intramolecular Electrophilic Addition of Arylsilanes to (r7 -1{dehyde)Ni(0) 83
Complex
９７
Conclusion

９９
List of Publications
Abbreviations
The following abbreviations are used in the thesis.
anal. Elemental anaylsys
Ac
acetyl
aq. aqueous
Ar aryl
br broad
Bn
benzyl
Bu
butyl
cat. catalyst
Cf confer
CI chemical ionization
COd 1,5-cyclooctadiene
Cy cyclohexyl
C
temperature in degrees centigrade
d doublet
δ chemical shift ofNMR signal in ppm
EI electron ionization
eq. equation
equlv equivalent
Et ethyl
Et20 diethylether
GC
gas chromatography
h hour(s)
Hex
hexyl
HMBC
hetero-nuclear multiple-bond connectivity
HMQC
hetero-nuclear multiple quantum coherence
HPLC
high-perfonnance liquid chromatography
HRPIS hi gh-resolution mass specra
Hz
hertz
J iso
IR infrared spectroscopy
」 coupling constant in NMR
KIE kinetic isotope effect
L
ligand
M
metal
meta
“NIle methyl
nlln minute(s)
mL milliliter
μL microliter
MS
mass spectral
4 normal
NHC
l/-heterocyclic carbene
NMR
nuclear magnetic resonance
lV
ο ortho
側ＥＰ Oak Ridge therlnal ellipsoid p16t
′ para
Ｐｈ phenyl
Ｐｒ propyl
ＰＲ３ trialkyl― or triaryl―phosphine
q quartet
quant quantitative
ref refcrence
RT room temperature
S singlet
sept septet
sext sextet
t triplet
Tf trinuoromethylsulfonyl
THF tetrahydrottan
TMS
trimethylsilyl
t triplet
Vl
I
Chapter
General Introduction