Heterogeneous Organic Base-Catalyzed Reactions Enhanced by Acid Supports

Motokura, Ken; Tada, Mizuki; Iwasawa, Yasuhiro

doi:10.1021/ja0704333

Cited by 140 publications

(104 citation statements)

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“…Alternatively, we recently reported a new strategy for the design of acid-base bifunctional catalyst surfaces: [2] 1) the utilization of strong solid acids as supports for increased catalytic activity, 2) the immobilization of tertiary amines on these supports for the expansion of applicable catalytic reactions, and 3) the use of silane-coupling reactions between the amine reagents and acidic solid supports to simplify the catalyst preparation. Herein, we report detailed studies on the synthesis and characterization of amorphous silica-alumina-supported amine catalysts and their application to various catalytic organic reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction [Eqs.…”

Section: And 29mentioning

confidence: 99%

“…[1] In addition to the increasing activity of the immobilized species, cooperative catalysis of the support surfaces with the immobilized species is another advantage of the use of supports. [2] The generation of multicatalytic functions on a solid surface realizes one-pot catalytic reaction sequences and double catalytic activation in a single reaction step for the improvement of the reaction rate and selectivity. [2,3] Acid-base dual-activation catalysis has received much attention for highly efficient nucleophilic reactions, including carbon-carbon bond-forming reactions.…”

Section: Introductionmentioning

confidence: 99%

“…[2] The generation of multicatalytic functions on a solid surface realizes one-pot catalytic reaction sequences and double catalytic activation in a single reaction step for the improvement of the reaction rate and selectivity. [2,3] Acid-base dual-activation catalysis has received much attention for highly efficient nucleophilic reactions, including carbon-carbon bond-forming reactions. [4] In base-catalyzed carbon-carbon couplings, nucleophilic precursors are activated by basic catalysts to generate nucleophiles by abstraction of their acidic parts, such as acyl groups and a-hydrogen atoms, and then, the nucleophiles attack electrophiles.…”

Section: Introductionmentioning

confidence: 99%

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Acid–Base Bifunctional Catalysis of Silica–Alumina‐Supported Organic Amines for Carbon–Carbon Bond‐Forming Reactions

Motokura

Tomita

Tada

et al. 2008

Chemistry A European J

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Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

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Section: And 29mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Acid–Base Bifunctional Catalysis of Silica–Alumina‐Supported Organic Amines for Carbon–Carbon Bond‐Forming Reactions

Motokura

Tomita

Tada

et al. 2008

Chemistry A European J

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“…Catalytic cascades, in which the product of a reaction catalyzed by species A undergoes a subsequent distinct transformation catalyzed by a second species B, are hindered by the possibility of undesired interactions between the initial substrate and the second active site, or indeed between the two catalytic species 20 . Such highly desirable 'one-pot' catalytic cascades therefore necessitate the spatial separation of each catalytic step.…”

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Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

et al. 2015

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. (2016) 'Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions.', Nature materials., 15 (2). pp. 178-182.Further information on publisher's website:Publisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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“…20,21 Solid-state 13 C and 29 Si NMR analyses of the tertiary amine-adsorbed intermediate and final immobilized catalyst revealed the following immobilization process for the amino functionality onto the SiO 2 -Al 2 O 3 surface. First, the amine group in the silane-coupling reagent interacts strongly with …”

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Development of Multiactive Site Catalysts for Surface Concerted Catalysis Aimed at One-Pot Synthesis

Motokura¹

2016

Bulletin of the Chemical Society of Japan

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). His research interests include precise design of multiactive sites on a catalytic surface, detailed characterization of active site environments, and establishment of the "concept of concerted catalysis on surface" for creating novel catalysis and molecular transformation. AbstractMultiactive site catalysts have been developed for conducting one-pot synthesis and highly efficient reactions based on the principle of concerted catalysis. Ru-grafted hydrotalcite containing both Ru and base sites on its outer surface exhibits high catalytic activity for the one-pot synthesis of dinitrile compounds. A reaction system consisting of a strong acid, base, and Pd species is capable of catalyzing a one-pot process consisting of five successive reactions, esterification, deacetalization, aldol reaction, hydrogenation, and Michael reaction, to produce a final product, 2,4-dicyanoester, from starting materials containing cycnoacetic acid and acetal, with excellent overall yield. Immobilization of an amine base onto a solid acid surface affords an acidbase bifunctional catalytic surface with controlled acidbase interactions. Various nucleophilic addition reactions including the one-pot synthesis of dinitroalkane derivatives proceeds effectively by acidbase concerted catalysis. The concept of concerted catalysis on solid surfaces can be extended to synergistic/double-activation catalysis between a metal complex and organic base immobilized on a surface. Further, the concept of multiactive site catalysis can also be applied to a homogeneous catalyst system. For example, a Cu-bisphosphine complex exhibits excellent catalytic performance for the transformation of CO 2 to valuable chemicals, such as cyclic carbonate, silyl formate, and formamides.

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Heterogeneous Organic Base-Catalyzed Reactions Enhanced by Acid Supports

Cited by 140 publications

References 14 publications

Acid–Base Bifunctional Catalysis of Silica–Alumina‐Supported Organic Amines for Carbon–Carbon Bond‐Forming Reactions

Acid–Base Bifunctional Catalysis of Silica–Alumina‐Supported Organic Amines for Carbon–Carbon Bond‐Forming Reactions

Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

Development of Multiactive Site Catalysts for Surface Concerted Catalysis Aimed at One-Pot Synthesis

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