New Horizons of Process Chemistry: Scalable Reactions and Technologies

285 Pages·2017·8.33 MB·English

by  Kiyoshi Tomioka

Kiyoshi Tomioka · Takayuki Shioiri
Hironao Sajiki E ditors
New Horizons
of Process
Chemistry
Scalable Reactions and Technologies
New Horizons of Process Chemistry
Kiyoshi Tomioka Takayuki Shioiri
(cid:129)
Hironao Sajiki
Editors
New Horizons of Process
Chemistry
Scalable Reactions and Technologies
123
Editors
Kiyoshi Tomioka Hironao Sajiki
DoshishaWomen’s Collegeof LiberalArts GifuPharmaceutical University
Kyotanabe Gifu
Japan Japan
Takayuki Shioiri
Meijo University
Nagoya
Japan
ISBN978-981-10-3420-6 ISBN978-981-10-3421-3 (eBook)
DOI 10.1007/978-981-10-3421-3
LibraryofCongressControlNumber:2016963739
©SpringerNatureSingaporePteLtd.2017
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Preface
Process chemistry will be one of the most important sciences in the twenty-first
century.Itpassesthebatoninarelayracefromdiscoveryofusefulnewmaterialsto
their industrial production. Economic and environmentally benign procedures are
essential. Because the stagnation of process chemistry is estimated to cause
industrial depression and excessive loss, chemists focus on process chemistry
consistently to provide a stimulus by the development of novel and efficient new
methods, reactions, and technologies applicable to scalable production.
In December 2015, the International Chemical Congress of Pacific Basin
Societies 2015 (Pacifichem 2015) was held in Hawaii, and the symposium
“NewHorizonofProcessChemistrybyScalableReactionsandTechnologies”was
convened as one of the technical programs, supported by the Japanese Society for
Process Chemistry. A series of interesting lectures by 35 speakers was delivered,
and 33 topics were presented at the poster session. Topics of these lectures and
presentations included new catalysts, reactions, and methods for the synthesis of
functional materials including pharmaceuticals, agrochemicals, chemical raw
materials, and other materials oriented toward process chemistry, with green and
sustainable chemistry as one of the major topics. Furthermore, various isolation
methods including crystallization, development of reactors and equipment, direct
observational methods of the progress in reactions, and process design to increase
scale were also important topics.
Thisbookisaselectionoftheabove-mentionedpresentations;however,itisnot
a proceedings of the symposium but rather a collection of mini-reviews based on
the presentations. Readers will be able to enjoy reading about the latest develop-
ments in the field of process chemistry, new methodology intended for process
chemistry, and medicinal chemistry.
Wehopeprocesschemistrywillbemoreproductiveandwillflourishinthenear
future.
Kyotanabe, Japan Kiyoshi Tomioka
Nagoya, Japan Takayuki Shioiri
Gifu, Japan Hironao Sajiki
v
Contents
Recent Advances in Rare Earth Metal Asymmetric Catalysis
Toward Practical Synthesis of Therapeutics.. .... .... .... ..... .... 1
Naoya Kumagai and Masakatsu Shibasaki
Metal Catalyzed Synthetic Reactions via Aerobic Oxidation
as a Key Step . .... .... .... ..... .... .... .... .... .... ..... .... 11
Mitsuru Shindo and Kenji Matsumoto
Heterogeneous Platinum Metal Catalyzed Deuterium
Generation and Labeling Methods Using Hydrogen Gas
and Deuterium Oxide as Key Reagents.. .... .... .... .... ..... .... 29
Hironao Sajiki
Pd on Spherical Carbon (Pd/SC)-Catalyzed Chemoselective
Hydrogenation. .... .... .... ..... .... .... .... .... .... ..... .... 41
Hiroyoshi Esaki
Environment-Friendly Iron-Catalyzed Reactions .. .... .... ..... .... 51
Yoshinari Sawama
Tetranuclear Zinc Cluster-Catalyzed Transesterification.... ..... .... 65
Takashi Ohshima
Vinyl Ruthenium Carbenes: Valuable Intermediates in Catalysis.. .... 89
Damián Padín, Jesús A. Varela and Carlos Saá
Radical-Based Late Stage C–H Functionalization
of Heteroaromatics in Drug Discovery .. .... .... .... .... ..... .... 103
Yuta Fujiwara and Phil S. Baran
Magnetic Nanoparticle-Supported Iodoarene Oxidative
Catalysts and Its Application to Phenol Oxidation. .... .... ..... .... 121
Hisanori Nambu, Ikumi Shimokawa, Tomoya Fujiwara
and Takayuki Yakura
vii
viii Contents
Recent Development of Diphenyl Phosphorazidate (DPPA)
as a Synthetic Reagent .. .... ..... .... .... .... .... .... ..... .... 131
Takayuki Shioiri
Methylenation Reaction of Carbonyl Compounds Using
Julia-Kocienski Reagents .... ..... .... .... .... .... .... ..... .... 147
Kaori Ando
Development of Shelf-Stable Reagents for Electrophilic
Trifluoromethylthiolation Reaction . .... .... .... .... .... ..... .... 163
Zhongyan Huang and Norio Shibata
Practical and Environmentally Friendly Transformation
of Tetrahydrofuran-2-Methanols to c-Lactones via Oxidative
Cleavage . .... .... .... .... ..... .... .... .... .... .... ..... .... 179
Tomoya Fujiwara, Yuto Horiuchi, Akihiro Yamada,
Hisanori Nambu and Takayuki Yakura
Five Step Asymmetric Total Synthesis of b-Lycorane Employing
Chiral Diether Ligand-Controlled Conjugate Addition-Michael
Reaction Cascade .. .... .... ..... .... .... .... .... .... ..... .... 191
Kiyoshi Tomioka
Concise Synthesis of Peptide Analogs Using a Fluorous-Fmoc
Protection Strategy. .... .... ..... .... .... .... .... .... ..... .... 201
Masato Matsugi
A Challenging Synthesis of the Highly Functionalized
Echinocandin ASP9726: A Successor of Micafungin—How Can
We Achieve the Large-Scale Synthesis? . .... .... .... .... ..... .... 217
Shinya Yoshida, Joji Hayashida, Yasuhiro Morinaga, Shoji Mizobata,
Akihiro Okada, Kazumi Kawai, Shinjirou Tanoue, Tomohide Nakata,
Minoru Kitayama, Atsushi Ohigashi, Mitsutaka Matsuura,
Takumi Takahashi, Shigeru Ieda and Minoru Okada
The Role of Silyl Protecting Group for the Synthesis
of Procyanidins and Their Derivatives .. .... .... .... .... ..... .... 229
Noriyuki Nakajima and Akiko Saito
Chemical Modification of the 3′-Dangling End of Small
Interfering RNAs Such as siRNAs and miRNAs:
The Development of miRNA Replacement Therapy.... .... ..... .... 237
Yukio Kitade, Takashi Mori and Yukihiro Akao
Contents ix
AntiviralAgentsTowardsChikungunyaVirus:Structures,Syntheses,
and Isolation from Natural Sources. .... .... .... .... .... ..... .... 251
Jih Ru Hwu, Tapan K. Pradhan, Shwu-Chen Tsay, Mohit Kapoor,
Sergey O. Bachurin, Oleg A. Raevsky and Johan Neyts
Analytical Standards Purity Determination Using Quantitative
Nuclear Magnetic Resonance. ..... .... .... .... .... .... ..... .... 275
Toru Miura, Naoki Sugimoto, Takako Suematsu, Kevin K. Millis,
Katsuo Asakura and Yuko Yamada
Recent Advances in Rare Earth Metal
Asymmetric Catalysis Toward Practical
Synthesis of Therapeutics
Naoya Kumagai and Masakatsu Shibasaki
Abstract Two case studies regarding the development of rare earth metal-based
asymmetric catalysts are summarized, with particular focus on the process of
refiningcatalystsamenabletoindustrialapplications.Amide-basedchiralligandsin
combination with lanthanum or neodymium cations furnished robust catalytic
systems for asymmetric amination or nitroaldol reactions, respectively. Although
rare earth metal catalysis is generally characterized by a peculiar coordination
chemistry and Lewis acidic catalytic functions, its wide availability and moderate
tolerancetomoisturearealsoimportantfeaturestobenoted,makingtheapplication
of rare earth metal catalysis beneficial for industrial large-scale synthesis.
(cid:1) (cid:1) (cid:1) (cid:1)
Keywords Amination Asymmetriccatalysis Flowreaction Nitroaldol Rare
earth metals
1 Introduction
Homochirality has become an indispensable feature for the manufacture of active
pharmaceutical ingredients (APIs), attracting increasing attention to enantioselec-
tive catalysis in medicinal and process chemistry as an efficient method for pro-
ducing chiral building blocks of interest. Efficiency in lab-scale synthesis and
feasibility in large-scale operations, however, are often difficult to achieve in par-
allel; the majority of newly developed methods in enantioselective catalysis are
rarely applied to industrial applications. Particularly for chiral hard Lewis acid
catalysts,therequirementforrigorousdryingofthesubstratesandreaction vessels
to achieve high fidelity in the reaction severely hampers industrial application.
N.Kumagai(&)(cid:1)M.Shibasaki(&)
InstituteofMicrobialChemistry(BIKAKEN),3-14-23Kamiosaki,
Shinagawa-kuTokyo141-0021,Japan
e-mail:[email protected]
M.Shibasaki
e-mail:[email protected]
©SpringerNatureSingaporePteLtd.2017 1
K.Tomiokaetal.(eds.),NewHorizonsofProcessChemistry,
DOI10.1007/978-981-10-3421-3_1
2 N.KumagaiandM.Shibasaki
Herein we document chiral rare earth metal catalysts that are promising for
prospective applicationin large-scaleindustrial operations. Despitethe term ‘rare’,
not all ‘rare’ earth metal are expensive and available in only small quantities [1];
indeed, the natural abundance of lanthanum, one of the most representative rare
earthmetals,intheearth’scrustisclosetothatofzincorboron.Therelativelylow
toxicity concerns of rare earth metals are also favorable for application to the
manufacture of APIs. This chapter summarizes two rare earth metal-based asym-
metric catalysts featuring lanthanum and neodymium as key components respon-
sible for catalytic functions.
2 La-based Catalysis: Catalytic Asymmetric Amination
Nitrogen is a key element embedded in carbon-based skeletons in a myriad of
natural products and therapeutics, thereby the development of synthetic method-
ologies to incorporate nitrogen functionalities have been a sustained topic in
organic synthesis. Electrophilic amination utilizing azodicarboxylates as elec-
trophiles is commonly exploited to install nitrogen functionality in certain nucle-
ophiles, including latent enolates [2]. Despite its early discovery [3–5], no
enantioselective variants were reported until Evans et al. disclosed catalytic
asymmetric a-amination of N-acyloxazolidines and enolsilanes promoted by Mg
and Cu complexes in the late 90s [6, 7]. Since this demonstration of enantiose-
lective introduction of nitrogen functionality, the flurry of reports on catalytic
asymmetricaminationappearedbased onbothorganocatalystsandmetalcatalysts,
and has been compiled in various review articles [8–12].
In this context, we were particularly intrigued by the fact that simple
succinimide-typesubstrate1eludedtheintroductionofanitrogenfunctionalityina
catalyticandenantioselectivemanner(Scheme 1).Aminationproduct2isaknown
key intermediate of ranirestat(AS-3201)[13, 14],whichis under clinical trials led
by Dainippon-Sumitomo Pharma for the treatment of diabetic neuropathy.
Previously identified organocatalysts and metal-based catalysts in the literature
Scheme1 Catalytic asymmetric amination of succinimide derivative 1 for the enantioselective
synthesisofranirestat,acandidatedrugfordiabeticneuropathy