ROMPgel Reagents in Parallel Synthesis

Barrett, Anthony G. M.; Hopkins, Brian T.; Köbberling, J.

doi:10.1021/cr0103423

Cited by 139 publications

(74 citation statements)

References 127 publications

(254 reference statements)

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“…As a result, many useful reagents that are well established in the field of solution-phase chemistry have been applied to immobilized reagents. [1][2][3][4][5][6][7][8][9] There have been some recent reports on the preparation of immobilized reagents for dehydrocondensation.10-18) However, since most of these reagents are immobilized by connecting dehydrocondensing reagents to insoluble carriers such as polystyrene and silica gel, they would be prepared by inefficient chemical transformation on the insoluble carrier under heterogeneous conditions. In addition, the weight proportion of the solid carrier relative to the amount of solidsupported reagent is generally high, which inevitably results in the generation of large amounts of waste; this is a serious problem common to solid-supported reagents.…”

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confidence: 99%

mentioning

confidence: 99%

“…As a result, many useful reagents that are well established in the field of solution-phase chemistry have been applied to immobilized reagents. [1][2][3][4][5][6][7][8][9] There have been some recent reports on the preparation of immobilized reagents for dehydrocondensation. [10][11][12][13][14][15][16][17][18] However, since most of these reagents are immobilized by connecting dehydrocondensing reagents to insoluble carriers such as polystyrene and silica gel, they would be prepared by inefficient chemical transformation on the insoluble carrier under heterogeneous conditions.…”

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confidence: 99%

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Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

et al. 2007

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The advance in combinatorial chemistry has resulted in the development of solid-supported reagents that can be applied to automated synthesis of a target molecule. As a result, many useful reagents that are well established in the field of solution-phase chemistry have been applied to immobilized reagents. [1][2][3][4][5][6][7][8][9] There have been some recent reports on the preparation of immobilized reagents for dehydrocondensation.10-18) However, since most of these reagents are immobilized by connecting dehydrocondensing reagents to insoluble carriers such as polystyrene and silica gel, they would be prepared by inefficient chemical transformation on the insoluble carrier under heterogeneous conditions. In addition, the weight proportion of the solid carrier relative to the amount of solidsupported reagent is generally high, which inevitably results in the generation of large amounts of waste; this is a serious problem common to solid-supported reagents. To resolve this issue, we developed a new immobilized triazine-type dehydrocondensing reagent by polymerizing the dehydrocondensing reagent itself.19) This polymer reagent is based on the condensing agent, 4,6-dimethoxy-1,3,5-triazinyl-2-methylmorpholinium chloride (DMT-MM) [20][21][22][23][24][25][26] and is a crosslinked polymer prepared by co-polymerizing tetra(ethylene glycol) bis(4-chloro-6-methoxy-1,3,5-triazin-2-yl) ether and tris(2-aminoethyl)amine, which is easily substituted onto the triazine ring under weakly basic conditions.In this work, we developed another application for polymer-type triazine condensing reagents: immobilization by well-established ROMP (ring opening metathesis polymerization) method, in which the reaction proceeds rapidly and with high yield under mild neutral conditions. The dramatically expanded ROMP methodology, based on the work of Grubbs et al. in the 1990s, has been developed as an effective method for acquiring high-loading polymer reagents by polymerizing the reagent unit as a monomer.27-31) Barrett et al. actively developed ROMP-gel supported reagents using this methodology, and reported many excellent immobilized reagents. 4,9,[32][33][34] These reagents have several advantages in addition to high-loading, e.g., high tolerance of the methathesis catalysts for diverse functionalities, and readily available monomers from inexpensive precursors. Recently, ROMP supported coupling reagents carrying fluoroformamidinium or 2-bromopyridinium were also reported.11) In this case, however, preparation of the monomers, which requires operation of 3-4 steps, seems not to be very easy.Our monomer 1a was readily prepared by reacting cyanuric chloride consecutively with 5-norbornene-2-methanol and MeOH (Chart 1). A CH 2 Cl 2 solution of the resulting monomer and cross-linker 2 35) in a mixing ratio of p : q, as shown in Table 1, was allowed to react in the presence of 0.1 mol% Grubbs' catalyst 3 to produce four kinds of polymer with cross-linking percentages of 10, 30, 50 and 100%. The polymer reagents exhibited condensation activ...

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confidence: 99%

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confidence: 99%

“…As a result, many useful reagents that are well established in the field of solution-phase chemistry have been applied to immobilized reagents. [1][2][3][4][5][6][7][8][9] There have been some recent reports on the preparation of immobilized reagents for dehydrocondensation. [10][11][12][13][14][15][16][17][18] However, since most of these reagents are immobilized by connecting dehydrocondensing reagents to insoluble carriers such as polystyrene and silica gel, they would be prepared by inefficient chemical transformation on the insoluble carrier under heterogeneous conditions.…”

mentioning

confidence: 99%

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Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

et al. 2007

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“…To force the DCPD system into a 3D cross-linked network morphology, and thus to increase both viscosity and strength at the sol-gel transition, we tested the addition of appropriate cross-linkers. 21 Preliminary results were very promising, and showed the formation of homogeneous, transparent thins gel films in the rotating cylinder test geometry. An alternative explanation may be the limited solubility of the DCPD polymer network in toluene.…”

Section: Hydrocarbon Aerogelsmentioning

confidence: 96%

Final report SI 08-SI-004: Fusion application targets

Biener¹,

Kucheyev²,

Wang³

et al. 2010

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“…Although chromatographic purification protocols have been optimized for decreasing the Ru content in the product to an almost acceptable level, the utilization of tagged reagents [3] and catalysts [4,5] is a far superior strategy. Indeed, it has seen a dramatic increase in interest.…”

Section: Introductionmentioning

confidence: 99%

Sustainable Concepts in Olefin Metathesis

et al. 2007

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Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerization reactions, only a limited number of industrial processes use olefin metathesis. This is mainly due to difficulties associated with removing ruthenium from the final products. In this context, a number of studies have been carried out to develop procedures for the removal of the catalyst or the products of catalyst decomposition, however, none are universally attractive so far. This situation has resulted in tremendous activity in the area dealing with supported or tagged versions of homogeneous catalysts. This Review summarizes the numerous studies focused on developing cleaner ruthenium-catalyzed metathesis processes.

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ROMPgel Reagents in Parallel Synthesis

Abstract: A. ROMPgel-Supported Horner−Emmons ReagentsThe first supported reagents to be published 67 were the phosphite ROMPgels 32 (R ) CO 2 Et, CN), which Scheme 2. Hydrogenation of the Polymer Backbone a a Reagents and conditions: (a) H2, Rh(PPh3)3Cl, PhH, 200 psi.

Cited by 139 publications

References 127 publications

Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

Final report SI 08-SI-004: Fusion application targets

Sustainable Concepts in Olefin Metathesis

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