Yasuhiro Uozumi

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Organization: Institute for Molecular Science

Department: RIKEN Center for Sustainable Resource Science, Wako, Saitama 351-0198, Japan

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TOPICS

Physical Chemistry

heterogenous catalysis

Chemicals
References

Batch and Continuous-Flow Huisgen 1,3-Dipolar Cycloadditions with an Amphiphilic Resin-Supported Triazine-Based Polyethyleneamine Dendrimer Copper Catalyst

Co-reporter:Shiguang Pan, Shuo Yan, Takao Osako, and Yasuhiro Uozumi

ACS Sustainable Chemistry & Engineering November 6, 2017 Volume 5(Issue 11) pp:10722-10722

Publication Date(Web):September 22, 2017

DOI:10.1021/acssuschemeng.7b02646

A polystyrene–poly(ethylene glycol) (PS–PEG) resin-supported triazine-based polyethyleneamine dendrimer copper catalyst (PS–PEG-TD2–CuSO4) was prepared and characterized by means of CP-MAS NMR, UV–vis/NIR, FTIR, SEM-EDX, XPS, and ICP-AES analyses. PS–PEG-TD2–CuSO4 was highly active in the Huisgen 1,3-dipolar cycloaddition of various organic azides with alkynes in water as well as the three-component reaction of alkynes, alkyl bromides, and sodium azide under batch conditions to give the corresponding triazoles in excellent yields with high recyclability of the catalyst. TEM analysis suggested that the copper nanoparticles generated in situ through reduction of PS–PEG-TD2–CuSO4 with sodium ascorbate serve as the active catalytic species. The application of PS–PEG-TD2–CuSO4 catalyst in a continuous-flow Huisgen reaction for the synthesis of 1,2,3-triazoles was also examined. The cycloaddition of organic azides with alkynes was completed within 22 s in the continuous-flow system containing PS–PEG-TD2–CuSO4 to give the corresponding triazoles in up to 99% yield. Moreover, the continuous-flow system accomplished the long-term continuous-flow cycloaddition for 48 h producing 10 g of a triazole as well as the successive flow reaction producing various kinds of triazoles.Keywords: Alkyne−azide cycloaddition; Aqueous reaction; Batch reaction; Continuous-flow reaction; Copper; Heterogeneous catalysis;

A palladium NNC-pincer complex: an efficient catalyst for allylic arylation at parts per billion levels

Co-reporter:Go Hamasaka, Fumie Sakurai and Yasuhiro Uozumi

Chemical Communications 2015 vol. 51(Issue 18) pp:3886-3888

Publication Date(Web):29 Jan 2015

DOI:10.1039/C4CC09726B

Allylic arylation of allylic acetates by sodium tetraarylborates in the presence of ppb to ppm (molar) loadings of a palladium NNC-pincer complex catalyst in methanol at 50 °C gave the corresponding arylated products in excellent yields. Total turnover numbers of up to 500000000 and turnover frequencies of up to 11250000 h−1 were achieved.

Development of an aquacatalytic system based on the formation of vesicles of an amphiphilic palladium NNC-pincer complex

Co-reporter:Fumie Sakurai, Go Hamasaka and Yasuhiro Uozumi

Dalton Transactions 2015 vol. 44(Issue 17) pp:7828-7834

Publication Date(Web):20 Mar 2015

DOI:10.1039/C5DT00434A

Two amphiphilic palladium NNC-pincer complexes bearing hydrophilic tri(ethylene glycol) chains and hydrophobic dodecyl chains were designed and prepared for the development of a new aquacatalytic system. In water, these amphiphilic complexes self-assembled to form vesicles, the structures which were established by means of a range of physical techniques. When the catalytic activities of the vesicles were investigated in the arylation of terminal alkynes in water, they were found to catalyze the reaction of aryl iodides with terminal alkynes to give good yields of the corresponding internal alkynes. The formation of a vesicular structure was shown to be essential for efficient promotion of this reaction in water.

Aerobic flow oxidation of alcohols in water catalyzed by platinum nanoparticles dispersed in an amphiphilic polymer

Co-reporter:Takao Osako, Kaoru Torii and Yasuhiro Uozumi

RSC Advances 2015 vol. 5(Issue 4) pp:2647-2654

Publication Date(Web):01 Dec 2014

DOI:10.1039/C4RA14947E

We have developed a technique for the aqueous aerobic flow oxidation of alcohols in a continuous-flow reactor containing platinum nanoparticles dispersed on an amphiphilic polystyrene–poly(ethylene glycol) resin (ARP-Pt). Various primary and secondary alcohols including aliphatic, aromatic and heteroaromatic alcohols were efficiently oxidized within 73 seconds in a flowing aqueous system at 100–120 °C under 40–70 bar of the system pressure to give the corresponding carboxylic acids and ketones, respectively, in up to 99% yield. Benzaldehydes could be also prepared selectively from benzyl alcohols by conducting the flow oxidation under the standard conditions in the presence of triethylamine. Moreover, a practical gram-scale synthesis of surfactants was realized in the aqueous aerobic continuous flow oxidation for 36–116 hours. This aerobic flow oxidation system provides a safe, clean, green, rapid and efficient practical method for oxidizing alcohols.

Brønsted acid-catalyzed selective C–C bond cleavage of 1,3-diketones: a facile synthesis of 4(3H)-quinazolinones in aqueous ethyl lactate

Co-reporter:Guanshuo Shen, Haifeng Zhou, Peng Du, Sensheng Liu, Kun Zou and Yasuhiro Uozumi

RSC Advances 2015 vol. 5(Issue 104) pp:85646-85651

Publication Date(Web):02 Oct 2015

DOI:10.1039/C5RA17969F

A facile and green approach was developed for the synthesis of 4(3H)-quinazolinones by using camphorsulfonic acid as a catalyst in an aqueous solution of biodegradable ethyl lactate. Various 2-aryl-, 2-alkyl-, and 2-(4-oxoalkyl)quinazolinones were obtained by cyclization of 2-aminobenzamides with a wide range of acyclic or cyclic 1,3-diketones via C–C bond cleavage in satisfactory to excellent yields.

Continuous-flow hydrogenation of olefins and nitrobenzenes catalyzed by platinum nanoparticles dispersed in an amphiphilic polymer

Co-reporter:Takao Osako, Kaoru Torii, Aya Tazawa and Yasuhiro Uozumi

RSC Advances 2015 vol. 5(Issue 57) pp:45760-45766

Publication Date(Web):15 May 2015

DOI:10.1039/C5RA07563G

A method for the flow hydrogenation of olefins and nitrobenzenes in a continuous-flow reactor containing platinum nanoparticles dispersed on an amphiphilic polystyrene–poly(ethylene glycol) resin (ARP-Pt) was developed. The hydrogenation of olefins and nitrobenzenes was completed within 31 seconds in the continuous-flow system containing ARP-Pt, giving the corresponding hydrogenated products in up to 99% yield with good chemoselectivity. Moreover, long-term (63–70 h) continuous-flow hydrogenation of styrene and nitrobenzene produced more than ten grams of ethylbenzene and aniline, respectively, without significant loss of catalytic activity. The flow hydrogenation system provides an efficient and practical method for the chemoselective reduction of olefins and nitrobenzenes.

A Convoluted Polymeric Imidazole Palladium Catalyst: Structural Elucidation and Investigation of the Driving Force for the Efficient MizorokiHeck Reaction

Co-reporter:Dr. Takuma Sato;Aya Ohno;Dr. Shaheen M. Sarkar;Dr. Yasuhiro Uozumi;Dr. Yoichi M. A. Yamada

ChemCatChem 2015 Volume 7( Issue 14) pp:2141-2148

Publication Date(Web):

DOI:10.1002/cctc.201500249

Abstract

MPPI-Pd (7 mol ppm Pd), prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and (NH₄)₂PdCl₄ by our molecular convolution method, promoted the Mizoroki–Heck reaction in water to give the corresponding coupling products with high yield and reusability. To clarify why the catalyst was so active, structural elucidation and temperature-dependent absorption/discharge investigation were performed using X-ray absorption fine structure analysis, Raman and far-IR spectroscopy, elemental analysis, and DFT calculations, which provided the structure of cis-PdCl₂L₂ (L=imidazole moiety). Moreover, the temperature-dependent absorption and discharge of aryl iodides and water in MPPI-Pd were observed with near-IR spectroscopy and macroscopic observations. The efficient diffusion of organic substrates into the internal nanospaces in MPPI-Pd and the following discharge of the water molecules at 80 °C should enhance the catalytic activity dramatically as the driving force of the reaction.

A vesicular self-assembled amphiphilic palladium NNC-pincer complex-catalyzed allylic arylation of allyl acetates with sodium tetraarylborates in water

Co-reporter:Go Hamasaka, Fumie Sakurai, Yasuhiro Uozumi

Tetrahedron 2015 Volume 71(Issue 37) pp:6437-6441

Publication Date(Web):16 September 2015

DOI:10.1016/j.tet.2015.04.108

The allylic arylation of various allyl acetates with sodium tetraarylborates proceeded in water in the presence of a vesicular self-assembled amphiphilic palladium NNC-pincer complex to give the corresponding arylated products in high yield, whereas the same complex as an amorphous powder did not promote the reaction efficiently. The formation of a vesicular structure was therefore shown to be essential for efficient promotion of the reaction.

Enantioposition-Selective Copper-Catalyzed Azide–Alkyne Cycloaddition for Construction of Chiral Biaryl Derivatives

Co-reporter:Takao Osako and Yasuhiro Uozumi

Organic Letters 2014 Volume 16(Issue 22) pp:5866-5869

Publication Date(Web):October 31, 2014

DOI:10.1021/ol502778j

A highly enantioposition-selective copper-catalyzed azide–alkyne cycloaddition (CuAAC) of dialkynes bearing prochiral biaryls has been developed for the construction of 1,2,3-triazoles bearing axially chiral biaryl groups in up to 76% yield and up to 99% ee.

Transfer hydrogenation of alkenes using Ni/Ru/Pt/Au heteroquatermetallic nanoparticle catalysts: sequential cooperation of multiple nano-metal species

Co-reporter:Yoshikazu Ito, Hidetoshi Ohta, Yoichi M. A. Yamada, Toshiaki Enoki and Yasuhiro Uozumi

Chemical Communications 2014 vol. 50(Issue 81) pp:12123-12126

Publication Date(Web):15 Aug 2014

DOI:10.1039/C4CC04559A

Quatermetallic alloy nanoparticles of Ni/Ru/Pt/Au were prepared and found to promote the catalytic transfer hydrogenation of non-activated alkenes bearing conjugating units (e.g., 4-phenyl-1-butene) with 2-propanol, where the composition metals, Ni, Ru, Pt, and Au, act cooperatively to provide significant catalytic ability.

Driving an equilibrium acetalization to completion in the presence of water

Co-reporter:Maki Minakawa, Yoichi M. A. Yamada and Yasuhiro Uozumi

RSC Advances 2014 vol. 4(Issue 69) pp:36864-36867

Publication Date(Web):13 Aug 2014

DOI:10.1039/C4RA07116F

Formation of an acetal from a carbonyl substrate by condensation with an alcohol is a classical reversible equilibrium reaction in which the water formed must be removed to drive the reaction to completion. A new method has been developed for acetalization of carbonyl substrates by diols in the presence of water. Complexation of poly(4-styrenesulfonic acid) with poly(4-vinylpyridine) generates a catalytic membrane of polymeric acid at the interface between two parallel laminar flows in a microchannel of a microflow reactor. The catalytic membrane provides a permeable barrier between the organic layer and water-containing layer in the reaction, and permits discharge of water to the outlet of the microreactor to complete the acetalization. Condensation of a variety of carbonyl substrates with diols proceeded in the presence of water in the microflow device to give the corresponding acetals in yields of up to 97% for residence times of 19 to 38 s.

Bimetallic Co–Pd alloy nanoparticles as magnetically recoverable catalysts for the aerobic oxidation of alcohols in water

Co-reporter:Yoshikazu Ito, Hidetoshi Ohta, Yoichi M.A. Yamada, Toshiaki Enoki, Yasuhiro Uozumi

Tetrahedron 2014 70(36) pp: 6146-6149

Publication Date(Web):

DOI:10.1016/j.tet.2014.03.108

Direct Dehydrative Esterification of Alcohols and Carboxylic Acids with a Macroporous Polymeric Acid Catalyst

Co-reporter:Maki Minakawa, Heeyoel Baek, Yoichi M. A. Yamada, Jin Wook Han, and Yasuhiro Uozumi

Organic Letters 2013 Volume 15(Issue 22) pp:5798-5801

Publication Date(Web):October 31, 2013

DOI:10.1021/ol4028495

A macroporous polymeric acid catalyst was prepared for the direct esterification of carboxylic acids and alcohols that proceeded at 50–80 °C without removal of water to give the corresponding esters with high yield. Flow esterification for the synthesis of biodiesel fuel was also achieved by using a column-packed macroporous acid catalyst under mild conditions without removal of water.

Amphiphilic Self-Assembled Polymeric Copper Catalyst to Parts per Million Levels: Click Chemistry

Co-reporter:Yoichi M. A. Yamada ; Shaheen M. Sarkar

Journal of the American Chemical Society 2012 Volume 134(Issue 22) pp:9285-9290

Publication Date(Web):May 15, 2012

DOI:10.1021/ja3036543

Self-assembly of copper sulfate and a poly(imidazole–acrylamide) amphiphile provided a highly active, reusable, globular, solid-phase catalyst for click chemistry. The self-assembled polymeric Cu catalyst was readily prepared from poly(N-isopropylacrylamide-co-N-vinylimidazole) and CuSO4 via coordinative convolution. The surface of the catalyst was covered with globular particles tens of nanometers in diameter, and those sheetlike composites were layered to build an aggregated structure. Moreover, the imidazole units in the polymeric ligand coordinate to CuSO4 to give a self-assembled, layered, polymeric copper complex. The insoluble amphiphilic polymeric imidazole Cu catalyst with even 4.5–45 mol ppm drove the Huisgen 1,3-dipolar cycloaddition of a variety of alkynes and organic azides, including the three-component cyclization of a variety of alkynes, organic halides, and sodium azide. The catalytic turnover number and frequency were up to 209000 and 6740 h–1, respectively. The catalyst was readily reused without loss of catalytic activity to give the corresponding triazoles quantitatively.

Self-Assembled Poly(imidazole-palladium): Highly Active, Reusable Catalyst at Parts per Million to Parts per Billion Levels

Co-reporter:Yoichi M. A. Yamada ; Shaheen M. Sarkar

Journal of the American Chemical Society 2012 Volume 134(Issue 6) pp:3190-3198

Publication Date(Web):January 16, 2012

DOI:10.1021/ja210772v

Metalloenzymes are essential proteins with vital activity that promote high-efficiency enzymatic reactions. To ensure catalytic activity, stability, and reusability for safe, nontoxic, sustainable chemistry, and green organic synthesis, it is important to develop metalloenzyme-inspired polymer-supported metal catalysts. Here, we present a highly active, reusable, self-assembled catalyst of poly(imidazole-acrylamide) and palladium species inspired by metalloenzymes and apply our convolution methodology to the preparation of polymeric metal catalysts. Thus, a metalloenzyme-inspired polymeric imidazole Pd catalyst (MEPI-Pd) was readily prepared by the coordinative convolution of (NH4)2PdCl4 and poly[(N-vinylimidazole)-co-(N-isopropylacrylamide)5] in a methanol–water solution at 80 °C for 30 min. SEM observation revealed that MEPI-Pd has a globular-aggregated, self-assembled structure. TEM observation and XPS and EDX analyses indicated that PdCl2 and Pd(0) nanoparticles were uniformly dispersed in MEPI-Pd. MEPI-Pd was utilized for the allylic arylation/alkenylation/vinylation of allylic esters and carbonates with aryl/alkenylboronic acids, vinylboronic acid esters, and tetraaryl borates. Even 0.8–40 mol ppm Pd of MEPI-Pd efficiently promoted allylic arylation/alkenylation/vinylation in alcohol and/or water with a catalytic turnover number (TON) of 20 000–1 250 000. Furthermore, MEPI-Pd efficiently promoted the Suzuki–Miyaura reaction of a variety of inactivated aryl chlorides as well as aryl bromides and iodides in water with a TON of up to 3 570 000. MEPI-Pd was reused for the allylic arylation and Suzuki–Miyaura reaction of an aryl chloride without loss of catalytic activity.

Development of Polymeric Palladium-Nanoparticle Membrane-Installed Microflow Devices and their Application in Hydrodehalogenation

Co-reporter:Dr. Yoichi M. A. Yamada;Dr. Toshihiro Watanabe;Aya Ohno;Dr. Yasuhiro Uozumi

ChemSusChem 2012 Volume 5( Issue 2) pp:293-299

Publication Date(Web):

DOI:10.1002/cssc.201100418

Abstract

We have developed a variety of polymeric palladium-nanoparticle membrane-installed microflow devices. Three types of polymers were convoluted with palladium salts under laminar flow conditions in a microflow reactor to form polymeric palladium membranes at the laminar flow interface. These membranes were reduced with aqueous sodium formate or heat to create microflow devices that contain polymeric palladium-nanoparticle membranes. These microflow devices achieved instantaneous hydrodehalogenation of aryl chlorides, bromides, iodides, and triflates by 10–1000 ppm within a residence time of 2–8 s at 50–90 °C by using safe, nonexplosive, aqueous sodium formate to quantitatively afford the corresponding hydrodehalogenated products. Polychlorinated biphenyl (10–1000 ppm) and polybrominated biphenyl (1000 ppm) were completely decomposed under similar conditions, yielding biphenyl as a fungicidal compound.

A novel amphiphilic pincer palladium complex: design, preparation and self-assembling behavior

Co-reporter:Go Hamasaka, Tsubasa Muto and Yasuhiro Uozumi

Dalton Transactions 2011 vol. 40(Issue 35) pp:8859-8868

Publication Date(Web):11 Aug 2011

DOI:10.1039/C1DT10556F

Amphiphilic pincer palladium complexes bearing hydrophilic and hydrophobic side chains on the planar NCN palladium pincer backbone were designed and prepared via the ligand introduction route. The complexes self-assembled under aqueous conditions to form vesicles with bilayer membranes containing palladium species. The catalytic activity of the vesicles in the Miyaura–Michael reaction in water was investigated.

Molecular-Architecture-Based Administration of Catalysis in Water: Self-Assembly of an Amphiphilic Palladium Pincer Complex

Co-reporter:Dr. Go Hamasaka;Tsubasa Muto;Dr. Yasuhiro Uozumi

Angewandte Chemie 2011 Volume 123( Issue 21) pp:4978-4980

Publication Date(Web):

DOI:10.1002/ange.201100827

A Highly Active and Reusable Self-Assembled Poly(Imidazole/Palladium) Catalyst: Allylic Arylation/Alkenylation

Co-reporter:Dr. Shaheen M. Sarkar;Dr. Yasuhiro Uozumi;Dr. Yoichi M. A. Yamada

Angewandte Chemie International Edition 2011 Volume 50( Issue 40) pp:9437-9441

Publication Date(Web):

DOI:10.1002/anie.201103799

Molecular-Architecture-Based Administration of Catalysis in Water: Self-Assembly of an Amphiphilic Palladium Pincer Complex

Co-reporter:Dr. Go Hamasaka;Tsubasa Muto;Dr. Yasuhiro Uozumi

Angewandte Chemie International Edition 2011 Volume 50( Issue 21) pp:4876-4878

Publication Date(Web):

DOI:10.1002/anie.201100827

A Highly Active and Reusable Self-Assembled Poly(Imidazole/Palladium) Catalyst: Allylic Arylation/Alkenylation

Co-reporter:Dr. Shaheen M. Sarkar;Dr. Yasuhiro Uozumi;Dr. Yoichi M. A. Yamada

Angewandte Chemie 2011 Volume 123( Issue 40) pp:9609-9613

Publication Date(Web):

DOI:10.1002/ange.201103799

Clean synthesis of triarylamines: Buchwald–Hartwig reaction in water with amphiphilic resin-supported palladium complexes

Co-reporter:Yoshinori Hirai and Yasuhiro Uozumi

Chemical Communications 2010 vol. 46(Issue 7) pp:1103-1105

Publication Date(Web):23 Dec 2009

DOI:10.1039/B918424D

Catalytic aromatic amination was achieved in water under heterogeneous conditions by the use of palladium complexes anchored to the amphiphilic PS-PEG resin with little palladium leaching to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines (TPDs).

Heterogeneous Aromatic Amination of Aryl Halides with Arylamines in Water with PS-PEG Resin-Supported Palladium Complexes

Co-reporter:Yoshinori Hirai

Chemistry – An Asian Journal 2010 Volume 5( Issue 8) pp:1788-1795

Publication Date(Web):

DOI:10.1002/asia.201000192

Abstract

Catalytic aromatic amination is achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. Aromatic amination of aryl halides with diphenylamine and N,N-double arylation of anilines with bromobenzene were found to proceed in water with broad substrate tolerance to give the triarylamines in high yield with high recyclability of the polymeric catalyst beads. Very little palladium leached from the polymeric catalyst under the water-based reaction conditions to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines (TPDs).

Cover Picture: Heterogeneous Aromatic Amination of Aryl Halides with Arylamines in Water with PS-PEG Resin-Supported Palladium Complexes (Chem. Asian J. 8/2010)

Co-reporter:Yoshinori Hirai

Chemistry – An Asian Journal 2010 Volume 5( Issue 8) pp:

Publication Date(Web):

DOI:10.1002/asia.201090024

Catalytic membrane-installed microchannel reactors for one-second allylic arylation

Co-reporter:Yoichi M. A. Yamada, Toshihiro Watanabe, Kaoru Torii and Yasuhiro Uozumi

Chemical Communications 2009 (Issue 37) pp:5594-5596

Publication Date(Web):18 Aug 2009

DOI:10.1039/B912696A

A variety of catalytic membranes of palladium-complexes with linear polymer ligands were prepared inside a microchannel reactor via coordinative and ionic molecular convolution to provide catalytic membrane-installed microdevices, which were applied to the instantaneous allylic arylation reaction of allylic esters and aryl boron reagents under microflow conditions to afford the corresponding coupling products within 1 second of residence time.

Asymmetric SuzukiMiyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin

Co-reporter:Yasuhiro Uozumi Dr.;Yutaka Matsuura Dr.;Takayasu Arakawa Dr.;YoichiM.A. Yamada Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 15) pp:2708-2710

Publication Date(Web):

DOI:10.1002/anie.200900469

Asymmetric SuzukiMiyaura Coupling in Water with a Chiral Palladium Catalyst Supported on an Amphiphilic Resin

Co-reporter:Yasuhiro Uozumi Dr.;Yutaka Matsuura Dr.;Takayasu Arakawa Dr.;YoichiM.A. Yamada Dr.

Angewandte Chemie 2009 Volume 121( Issue 15) pp:2746-2748

Publication Date(Web):

DOI:10.1002/ange.200900469

Development of an amphiphilic resin-dispersion of nanopalladium and nanoplatinum catalysts: Design, preparation, and their use in green organic transformations

Co-reporter:Yasuhiro Uozumi ;Yoichi M. A. Yamada

The Chemical Record 2009 Volume 9( Issue 1) pp:51-65

Publication Date(Web):

DOI:10.1002/tcr.20165

Abstract

An amphiphilic polymer resin-dispersion of nanoparticles of palladium was designed and prepared with a view toward use for catalysis in water. The amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-dispersion of nanoparticles of palladium exhibited high catalytic performance in the hydrodechlorination of chloroarenes under aqueous conditions. The amphiphilic resin-supported nanopalladium and nanoplatinum particles also catalyzed aerobic oxidation of various alcohols including nonactivated aliphatic and alicyclic alcohols, which is one of the most fundamental and important yet immature processes in organic chemistry, in water under an atmospheric pressure of oxygen gas to form aldehydes, ketones, and carboxylic acids to meet green chemical requirements. Viologen polymer-supported nanopalladium catalyst realized α-alkylation of ketones with primary alcohols as the alkylating agents. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 51–65; 2009: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20165

An Amphiphilic Resin-dispersion of Nanoparticles of Platinum (ARP-Pt): A Highly Active and Recyclable Catalyst for the Aerobic Oxidation of a Variety of Alcohols in Water

Co-reporter:Yoichi M.A. Yamada Dr.;Takayasu Arakawa Dr.;Heiko Hocke Dr. Dr.

Chemistry – An Asian Journal 2009 Volume 4( Issue 7) pp:1092-1098

Publication Date(Web):

DOI:10.1002/asia.200800478

Highly Efficient Heterogeneous Aqueous Kharasch Reaction with an Amphiphilic Resin-Supported Ruthenium Catalyst

Co-reporter:Yohei Oe

Advanced Synthesis & Catalysis 2008 Volume 350( Issue 11-12) pp:1771-1775

Publication Date(Web):

DOI:10.1002/adsc.200800359

Abstract

An amphiphilic polystyrene-polyethylene glycol (PS-PEG) resin-supported ruthenium complex was designed and prepared. The polymeric Ru complex was found to promote the transition metal-catalyzed atom transfer radical addition of halogenated compounds to olefins, the Kharasch reaction, in water under heterogeneous as well as AIBN-free conditions with a high level of atom economy to meet green chemical requirements.

Synthesis of [2,6-Bis(2-oxazolinyl)phenyl]palladium Complexes via the Ligand Introduction Route

Co-reporter:Tsutomu Kimura

Organometallics 2008 Volume 27(Issue 19) pp:5159-5162

Publication Date(Web):September 11, 2008

DOI:10.1021/om800666x

A series of [2,6-bis(2-oxazolinyl)phenyl]palladium (Phebox-Pd) complexes were synthesized via the ligand introduction route. trans-Bromo(2,6-dicarboxyphenyl)bis(triphenylphosphine)palladium was prepared by the reaction of 2-bromoisophthalic acid with Pd(PPh3)4 in 93% yield, and the carboxy groups of the palladium complex were converted into oxazolinyl groups to give the Phebox-Pd complexes in 44−57% yield.

Pd Pincer Complex as a Probe To Index the Coordination Ability of Various Ligands

Co-reporter:Maki Minakawa;Kazuhiro Takenaka

European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 12) pp:

Publication Date(Web):14 MAR 2007

DOI:10.1002/ejic.200700037

An NCN pincer palladium complex was developed as a probe molecule to index the coordination ability of various monodentate ligands. Coordination constants of 27 monodentate ligands (L) with a pincer palladium complex to form complexes of the type ArPd(L)₂Cl were determined by ¹H NMR spectroscopy. This allowed the coordination ability of a wide variety of ligands, including P-coordinating ligands (phosphane, phosphite), as well as As-coordinating AsPh₃, and N-coordinating pyridine, to be indexed. The differential between the highest/lowest coordination constants was 10¹². The relative coordination ability is described in a logarithmic manner, log(K_eq(L)/K_eq), with respect to the value of PPh₃ to exhibit high linearity in the Hammett plot.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

A Nanoplatinum Catalyst for Aerobic Oxidation of Alcohols in Water

Co-reporter:Yoichi M. A. Yamada Dr.;Takayasu Arakawa;Heiko Hocke Dr. Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 5) pp:

Publication Date(Web):13 DEC 2006

DOI:10.1002/anie.200603900

Aerobic exercise: A dispersion of nanoparticles of platinum in an amphiphilic polystyrene–polyethylene glycol resin (ARP-Pt) contains particles with a mean diameter of 5.9 nm and a narrow size distribution throughout the resin. ARP-Pt is a readily recyclable catalyst for the aerobic oxidation of a wide variety of alcohols in water with an oxygen or air atmosphere under heterogeneous conditions (see picture).

A Nanoplatinum Catalyst for Aerobic Oxidation of Alcohols in Water

Co-reporter:Yoichi M. A. Yamada Dr.;Takayasu Arakawa;Heiko Hocke Dr. Dr.

Angewandte Chemie 2007 Volume 119(Issue 5) pp:

Publication Date(Web):13 DEC 2006

DOI:10.1002/ange.200603900

Luftige Übung: Eine Dispersion von Platinnanopartikeln in einem amphiphilen Polystyrol-Polyethylenglycol-Harz (ARP-Pt) enthält Partikel mit einem mittleren Durchmesser von 5.9 nm und einer engen Größenverteilung im ganzen Harz. ARP-Pt ist ein einfach wiederverwendbarer Katalysator für die aerobe Oxidation von Alkoholen in Wasser mit reinem Sauerstoff oder mit Luft unter heterogenkatalytischen Bedingungen (siehe Bild).

A Combinatorial Approach to Heterogeneous Asymmetric Aquacatalysis with Amphiphilic Polymer-Supported Chiral Phosphine-Palladium Complexes

Co-reporter:Yukinari Kobayashi;Daiki Tanaka;Hiroshi Danjo

Advanced Synthesis & Catalysis 2006 Volume 348(Issue 12-13) pp:

Publication Date(Web):11 AUG 2006

DOI:10.1002/adsc.200606146

A library of amphiphlic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported chiral phosphine ligands was prepared by the split method using porous miniature reactors. A polymeric (R)-2-(diphenylphosphino)binaphthyl (MOP) ligand anchored onto the PS-PEG resin by an (S)-alanine tether unit was identified through the library-based screening to be an effective chiral ligand for the asymmetric palladium-catalyzed π-allylic substitution under heterogeneous aqueous conditions.

Asymmetric π-allylic etherification of cycloalkenyl esters with phenols in water using a resin-supported chiral palladium complex

Co-reporter:Yasuhiro Uozumi, Masahiro Kimura

Tetrahedron: Asymmetry 2006 Volume 17(Issue 1) pp:161-166

Publication Date(Web):9 January 2006

DOI:10.1016/j.tetasy.2005.11.026

Catalytic asymmetric etherification of cycloalkenyl esters with phenolic nucleophiles was achieved in water as the sole reaction medium under heterogeneous conditions by using 2 mol % palladium of a PS-PEG resin-supported palladium–imidazoindolephosphine complex to give optically active aryl(cycloalkenyl) ethers with up to 94% ee.(S)-Cyclohex-2-enyl 4′-methoxyphenyl etherC13H16O2Ee 86%[α]D25=-102.5 (c 1.3, dichloromethane)Source of chirality: asymmetric synthesisCyclopent-2-enyl 4′-methoxyphenyl etherC12H14O2Ee 84%[α]D25=-68.0 (c 1.0, dichloromethane)Source of chirality: asymmetric synthesis4′-Benzyloxyphenyl cyclohex-2-enyl etherC19H20O2Ee 85%[α]D25=-78.2 (c 1.2, dichloromethane)Source of chirality: asymmetric synthesis2′-Benzyloxyphenyl cyclohex-2-enyl etherC19H20O2Ee 88%[α]D25=-81.0 (c 1.0, dichloromethane)Source of chirality: asymmetric synthesis(S)-Cyclohept-2-enyl 4′-methoxyphenyl etherC14H18O2Ee 92%[α]D24=+3.4 (c 1.2, dichloromethane)Source of chirality: asymmetric synthesis4′-Benzyloxyphenyl cyclohept-2-enyl etherC20H22O2Ee 89%[α]D25=+7.4 (c 1.0, dichloromethane)Source of chirality: asymmetric synthesis2′-Benzyloxyphenyl cyclohept-2-enyl etherC20H22O2Ee 93%[α]D25=-8.1 (c 1.7, dichloromethane)Source of chirality: asymmetric synthesiscis-(5′-Methoxycarbonyl)cyclohex-2′-enyl 4-methoxyphenyl etherC15H18O4Ee 93%[α]D25=+5.9 (c 1.2, dichloromethane)Source of chirality: asymmetric synthesiscis-(5′-Methoxycarbonyl)cyclohex-2′-enyl 4-benzyloxyphenyl etherC21H22O4Ee 93%[α]D25=+7.1 (c 1.3, dichloromethane)Source of chirality: asymmetric synthesiscis-(5′-Methoxycarbonyl)cyclohex-2′-enyl 2-benzyloxyphenyl etherC21H22O4Ee 94%[α]D25=+1.0 (c 1.2, dichloromethane)Source of chirality: asymmetric synthesistert-Butyl 3-(4′-methoxyphenoxy)-1,2,3,6-tetrahydropyridine-1-carboxylateC17H23NO4Ee 94%[α]D25=-45.7 (c 0.8, dichloromethane)Source of chirality: asymmetric synthesistert-Butyl 3-(4′-benzyloxyphenoxy)-1,2,3,6-tetrahydropyridine-1-carboxylateC23H27NO4Ee 94%[α]D25=-34.7 (c 0.7, dichloromethane)Source of chirality: asymmetric synthesistert-Butyl 3-(2′-benzyloxyphenoxy)-1,2,3,6-tetrahydropyridine-1-carboxylateC23H27NO4Ee 92%[α]D25=-45.1 (c 0.7, dichloromethane)Source of chirality: asymmetric synthesis(R)-2′-(Cyclohex-2-enyl)-4′-methoxyphenolC13H16O2Ee 83%[α]D25=+95.0 (c 1.0, dichloromethane)Source of chirality: asymmetric synthesis(R)-2′-(Cyclohept-2-enyl)-4′-methoxyphenolC14H18O2Ee 90%[α]D25=+35.5 (c 1.1, dichloromethane)Source of chirality: asymmetric synthesis

An N-C-N Pincer Palladium Complex as an Efficient Catalyst Precursor for the Heck Reaction

Co-reporter:Kazuhiro Takenaka

Advanced Synthesis & Catalysis 2004 Volume 346(Issue 13-15) pp:

Publication Date(Web):16 DEC 2004

DOI:10.1002/adsc.200404161

The Heck reaction of iodobenzene and methyl acrylate took place smoothly in NMP at 140 °C in the presence of 1 mol ppb of the pincer palladium complex [4-tert-butyl-2,6-bis{(3R,7aS)-2-phenylhexahydro-1H-pyrrolo[1,2-c]imidazole-1-on-3-yl}phenyl]chloropalladium to give methyl cinnamate which corresponds to 520×10⁶ TON and 6500/sec TOF.

Catalytic Oxidation of Alcohols in Water under Atmospheric Oxygen by Use of an Amphiphilic Resin-Dispersion of a Nanopalladium Catalyst

Co-reporter:Yasuhiro Uozumi ;Ryu Nakao

Angewandte Chemie 2003 Volume 115(Issue 2) pp:

Publication Date(Web):16 JAN 2003

DOI:10.1002/ange.200390044

Der idealen Alkoholoxidation einen Schritt näher: Die katalytische Oxidation von Alkoholen in Wasser mit O₂ unter Atmosphärendruck wurde mit Pd-Nanokatalysatoren erreicht, die in einem amphiphilen Harz dispergiert sind (siehe Schema). Dieses Katalysatorsystem vereint in sich hohe katalytische Aktivität (bedingt durch die große Oberfläche der Nanopartikel) und Reaktivität in wässrigem Medium (dank der Amphiphilie der polymeren Matrix).

Catalytic Oxidation of Alcohols in Water under Atmospheric Oxygen by Use of an Amphiphilic Resin-Dispersion of a Nanopalladium Catalyst

Co-reporter:Yasuhiro Uozumi ;Ryu Nakao

Angewandte Chemie International Edition 2003 Volume 42(Issue 2) pp:

Publication Date(Web):16 JAN 2003

DOI:10.1002/anie.200390076

A step closer to the ideal oxidation of alcohols: Catalytic oxidation of alcohols in water under atmospheric oxygen was achieved by use of an amphiphilic resin-dispersion of a nanopalladium catalyst (see scheme). This system combines high catalytic activity owing to the large surface area of the nanoparticles and water-based reactivity provided by the amphiphilicity of the polystyrene—poly(ethylene glycol) matrix.

Amphiphilic Resin-Supported Rhodium-Phosphine Catalysts for C-C Bond Forming Reactions in Water

Co-reporter:Yasuhiro Uozumi;Maki Nakazono

Advanced Synthesis & Catalysis 2002 Volume 344(Issue 3-4) pp:

Publication Date(Web):13 JUN 2002

DOI:10.1002/1615-4169(200206)344:3/4<274::AID-ADSC274>3.0.CO;2-S

Amphiphilic resin-supported rhodium-phosphine complexes were prepared on polystyrene-poly(ethylene glycol) graft co-polymer (1% DVB cross-linked) beads. The immobilized rhodium complexes exhibited high catalytic activity in water to promote hydroformylation of 1-alkenes, [2+2+2] cyclotrimerization of internal alkynes forming benzene rings, and 1,4-addition of arylboronic acids.

New homochiral phosphine ligands having a hexahydro-1H-pyrrolo[1,2-c]imidazolone backbone: preparation and use for palladium-catalyzed asymmetric alkylation of cycloalkenyl carbonates

Co-reporter:Kazutaka Shibatomi, Yasuhiro Uozumi

Tetrahedron: Asymmetry 2002 Volume 13(Issue 16) pp:1769-1772

Publication Date(Web):27 August 2002

DOI:10.1016/S0957-4166(02)00467-6

New chiral ligands having a pyrrolo[1,2-c]imidazolone backbone were prepared by condensation of anilides of homochiral cyclic amino acids with 2-(diphenylphosphino)benzaldehyde. Of these ligands, (3R,9aS)-(3-(2-diphenylphosphino)phenyl-2-phenyl)tetrahydro-1H-imidazo[1,5-a]indole-1-one was found to be effective for palladium-catalyzed asymmetric allylic alkylation of cycloalkenyl carbonates with dimethyl malonate to give the corresponding dimethyl cycloalkenylmalonates with e.e. of up to 89%.Graphic(3R,7aS)-(3-(2-Diphenylphosphinophenyl)-2-phenyl)hexahydro-1H-pyrrolo[1,2-c]imidazol-1-oneC30H27N2OPE.e. >99%[α]D19=+44 (c 1.4, chloroform)Source of chirality: l-proline(3R,7aS)-(3-(2-Diphenylphosphino)phenyl-6-hydroxy-2-phenyl)hexahydro-1H-pyrrolo[1,2-c]imidazol-1-oneC30H27N2OPE.e. >99%[α]D19=+9 (c 1.6, chloroform)Source of chirality: trans-4-hydroxy-l-proline(3S,9aS)-(3-(2-Diphenylphosphino)phenyl-2-phenyl)tetrahydro-1H-imidazo[1,5-a]indole-1-oneC34H27N2OPE.e. >99%[α]D25=+135 (c 1.0, chloroform)Source of chirality: (S)-indoline-2-carboxylic acid(3S,9aS)-(3-(2-Diphenylphosphino)phenyl-2-phenyl)tetrahydro-1H-imidazo[1,5-a]indole-1-oneC34H27N2OPE.e. >99%[α]D19=+127 (c 0.7, chloroform)Source of chirality: (S)-indoline-2-carboxylic acid(3R,10aS)-(3-(2-Diphenylphosphino)phenyl-2-phenyl)tetrahydro-1H,5H-imidazo[1,5-b]isoquinoline-1-oneC35H29N2OPE.e. >99%[α]D25=+6 (c 0.5, chloroform)Source of chirality: (S)-1,2,3,4-tetrahydro-3-isoquinolinecarboxylic acid

A novel amphiphilic pincer palladium complex: design, preparation and self-assembling behavior

Co-reporter:Go Hamasaka, Tsubasa Muto and Yasuhiro Uozumi

Dalton Transactions 2011 - vol. 40(Issue 35) pp:NaN8868-8868

Publication Date(Web):2011/08/11

DOI:10.1039/C1DT10556F

Transfer hydrogenation of alkenes using Ni/Ru/Pt/Au heteroquatermetallic nanoparticle catalysts: sequential cooperation of multiple nano-metal species

Co-reporter:Yoshikazu Ito, Hidetoshi Ohta, Yoichi M. A. Yamada, Toshiaki Enoki and Yasuhiro Uozumi

Chemical Communications 2014 - vol. 50(Issue 81) pp:NaN12126-12126

Publication Date(Web):2014/08/15

DOI:10.1039/C4CC04559A

Clean synthesis of triarylamines: Buchwald–Hartwig reaction in water with amphiphilic resin-supported palladium complexes

Co-reporter:Yoshinori Hirai and Yasuhiro Uozumi