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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00277—Apparatus
  • B01J2219/00279—Features relating to reactor vessels
  • B01J2219/00306—Reactor vessels in a multiple arrangement
  • B01J2219/00313—Reactor vessels in a multiple arrangement the reactor vessels being formed by arrays of wells in blocks
  • B01J2219/00315—Microtiter plates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00277—Apparatus
  • B01J2219/00495—Means for heating or cooling the reaction vessels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00277—Apparatus
  • B01J2219/00497—Features relating to the solid phase supports
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00583—Features relative to the processes being carried out
  • B01J2219/00585—Parallel processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00583—Features relative to the processes being carried out
  • B01J2219/00596—Solid-phase processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00583—Features relative to the processes being carried out
  • B01J2219/00599—Solution-phase processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00583—Features relative to the processes being carried out
  • B01J2219/00603—Making arrays on substantially continuous surfaces
  • B01J2219/00659—Two-dimensional arrays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/0068—Means for controlling the apparatus of the process
  • B01J2219/00702—Processes involving means for analysing and characterising the products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00709—Type of synthesis
  • B01J2219/00713—Electrochemical synthesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00718—Type of compounds synthesised
  • B01J2219/0072—Organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
  • B01J2219/00759—Purification of compounds synthesised
• • C—CHEMISTRY; METALLURGY
  • C40—COMBINATORIAL TECHNOLOGY
  • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
  • C40B50/00—Methods of creating libraries, e.g. combinatorial synthesis
  • C40B50/08—Liquid phase synthesis, i.e. wherein all library building blocks are in liquid phase or in solution during library creation; Particular methods of cleavage from the liquid support
• • C—CHEMISTRY; METALLURGY
  • C40—COMBINATORIAL TECHNOLOGY
  • C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
  • C40B60/00—Apparatus specially adapted for use in combinatorial chemistry or with libraries
  • C40B60/14—Apparatus specially adapted for use in combinatorial chemistry or with libraries for creating libraries

Definitions

• the present invention is in the field of synthetic chemistry relating to combinatorial and high throughput chemical synthesis and is particularly concerned with an apparatus and method for combinatoral catalysis of chemical reactions and parallel synthesis.
• a long-standing challenge in this area is to control the fate of electrogenerated intermediates.
• One possible solution is to mediate electron transfer by immobilizing a catalytically active species in the diffusion layer. Such immobilization can be accomplished via formation of catalyst- impregnated films at the electrode surface or via covalent linking of the corresponding catalyst precursors to the electrode surface ( Figure 1).
• the present invention provides a spatially addressable multi-well electrode platform in order to perform electrosynthesis, electrocatalysis, as well as cyclic voltammetry (CV) measurements in a microtiter plate format.
• Each one of the reaction vessels in this novel piece of instrumentation comprises two parts: (a) miniwell equipped with a first electrode in the well, or cell and (b) complementary counterelectrode for insertion into the cell - one for each cell therby creating an electrode platform.
• the electrode platform becomes functional when mounted onto the miniwell array.
• the present invention provides an apparatus for conducting multiple electrosynthetic reactions simultaneously comprising: two or more cells; an electrode in each of said cells; a counter electrode for each of said electrodes; and an energy source coupled to provide energy to each pair of electrode and counter electrodes.
• the energy source provides galvanostatic conditions in each cell, and the electrode and counter electrode are either unmodified or are coated with a conducting polymer, preferably the conducting polymer is selected from functionalized polypyrrole, polythiophene, and copolymers thereof and the electrode and counter electrode are made from graphite, platinum, or ito glass.
• a conducting polymer is selected from functionalized polypyrrole, polythiophene, and copolymers thereof and the electrode and counter electrode are made from graphite, platinum, or ito glass.
• an apparatus according to the present invention is provided with miniwells in a plate format and an electrode, preferably the cathode is located at the bottom of the vessel and the counter electrode is located on a platform member.
• the present invention provides an apparatus for conducting multiple electrosynthetic reactions simultaneously comprising: 96 cells, preferably in a block made of teflon or glass; an anode electrode in each of said cells; a complementary cathode electrode attached to a common terminal each of which is for insertion into each of said cells; and an energy source coupled to provide energy to each pair of cathode electrode and anode electrodes.
• the method comprises the steps of: adding an appropriate quantity of electrolyte solution to each cell of an apparatus according to the present invention; adding an appropriate quantity of a substrate to each cell; adding an appropriate quantity of a reaction compound to each vessel; placing the apparatus in a medium to maintain temperature; conducting electrolysis; and isolating and characterizing any reaction products.
• the energy source according to the method provides galvanostatic conditions in each cell.
• the electrode and counter electrode are coated with a conducting polymer, most preferably the conducting polymer is selected from functionalized polypyrrole, polythiophene, and copolymers thereof.
• the electrode and counter electrode are made from graphite, platinum or ito glass, and the two or more cells are miniwells in a plate format.
• the electrode is located at the bottom of the vessel and the counter electrode is located on a platform member.
• the electrolyte solution is acetonitrile. Accordingly, practicing the methods of the invention provide for high throughput screening of diversely modified electrode surfaces and in a preferred format may lead to the discovery of new electrocatalytic systems through rapid optimization of parameters such as film composition, thickness, porosity, conductivity, and effective catalyst loading. Further, practicing the methods of the invention provide for facilitated rapid synthesis of diverse organic compounds.
• Figure 1 is a conceptual configuration of an electrode modified with an immobilized catalyst
• Figure 2 (a) illustrates 4x4 array of electrolysis cells as used in the Teflon block and glass vial embodiment of the invention before electrode assembly;
• Figure 2 (b) illustrates the 4x4 array of Figure 2(a) after electrode assembly
• Figure 3 illustrates a 96 well "microtitre plate” configuration of an electrode platform of the present invention
• Figure 4(a) illustrates a polypyrrole film deposition on the surface of an electrode according to the present invention (X indicates a spacer of variable length and ML n indicates a catalyst);
• Figure 4(b) illustrates copolymerization of pyrroles of Figure 4A covalently attached to an oxidized surface of an electrode of the present invention (X indicates a spacer of variable length and ML n indicates a catalyst);
• Figure 5(a) illustrates solution-phase chemistry for the parallel synthesis of the 3-substituted pyrrole library
• Figure 5(b) illustrates polypyrrole surface modification.
• EDC N-ethyl-
• N'-(dimethylaminopropyl)carbodiimide N'-(dimethylaminopropyl)carbodiimide
• NHS N-hydroxysuccinimide
• RNH2 electrocatalyst precursor
• Figure 6 illustrates the current density effect on reaction between a carbamate and methanol
• Figure 7 illustrates the temperature effect on reaction between a carbamate and methanol
• Figure 8 illustrates the content effect of acetonitrile on reaction between a carbamate and methanol
• Figure 9 illustrates the yield of parallel electrolysis of a number of substrates in a number of alcohols
• Figure 12 illustrates solution-phase chemistry of a reaction scheme for generating a library of substituted pyrroles
• Figure 13 illustrates an approach toward a library of PP/PT copolymer-based supports
• Figure 14 illustrates the solid phase synthesis of a library of reverse- turn peptidomimetics via two electrochemically controlled steps which are mixed with traditional chemical reactions: c. anodic oxidation; d. cathodic reduction; and
• Figure 15 illustrates the general methodology for the preparation of a library of conducting supports and their subsequent use in solid-phase synthesis.
• Electrochemistry is at the interface of solution and solid-phase chemistry as the electron transfer steps take place in the Helmholtz double layer at the electrode surface.
• Highly reactive intermediates such as radical- ions, radicals, carbanions and carbocations can be generated under very mild reaction conditions in that region.
• many well established electrosynthetic reactions proceed with little or no by-products.
• these processes often lead to compounds that are not readily accessible using traditional methodologies.
• Selected examples include Kolbe electrolysis and electrohydrodimerization (EHD), which give carbon-carbon bond formation in a manner difficult to match by other routes (Utley (1994)).
• EHD electrohydrodimerization
• Another advantage of electrosynthesis over conventional chemical methods is selective transformation of functional groups by controlling the applied potential.
• nitroalkanes can be selectively reduced to hydroxylamines or amines (Cyr et al. (1990)).
• Electrochemical methods were introduced in the field of combinatorial chemistry only recently by Smotkin and Mallouk in parallel screening of electrocatalysts (Reddington et al. (1998)).
• a 645-member electrode array containing five elements and their binary, ternary and quaternary combinations was screened in order to identify the most active alloy catalyst compositions for the electrooxidation of methanol.
• Protons generated at the anode were detected by a fluorescent acid-base indicator which was then correlated with catalytic activity.
• a handful of electrochemically generated solid supports and solid-phase electrochemical reactions appeared.
• the apparatus comprises a 16-well electrolysis platform. While two different types of electrolysis cells are described further here, it will be readily understood by those skilled in the art that the specific features described are not limiting and that there can be many variations to the invention of the apparatus. Such variations will be readily apparent to those skilled in the art. In one instance, a Teflon block with 16 wells drilled into it was used while in another a set of 16 glass vials was used.
• the spatially addressable electrolysis multiple cell apparatus 10 has 16 Teflon or cylindrical glass cells 20 arranged in a 4 by 4 array, each equipped with a tubular stainless-steel cathode 30 and a graphite rod anode 40.
• the stainless-steel cathodes were welded into a stainless-steel plate 50, which acts as a common terminal for the connection to a current source.
• the choice of graphite and stainless-steel for the anode and cathode is not limiting and as will be readily appreciated other materials may be used including carbon (felt, cloth, reticulated vitreous carbon, glassy carbon), platinum (rods, mesh foam), titanium (rods), ito glass, and mercury.
• the graphite anodes served as working electrodes and were insulated from each other and cathodes by planting through a Teflon plate. Parallel connection of the 16 cells was achieved using this set-up.
• a spatially addressable 96-well electrode platform in order to perform electrosynthesis as well as cyclic voltammetry (CV) measurements in a microtiter plate format (see Figure 3).
• a standard commercially available polypropylene plate may be used.
• Each one of the 96 reaction vessels in this embodiment of instrumentation of the invention comprises two main elements: (a) a miniwell 60 equipped with a graphite (or other suitable material) electrode preferably at the bottom (not shown); and (b) complementary counter electrode 70 comprising graphite or other suitable material or platinum pierced through a polypropylene plate 80.
• the electrode platform becomes functional when this plate is mounted onto the miniwell array.
• a DC power supply is used to run electrolyses under galvanostatic conditions and the total charge passed is determined by a digital coulometer. As is apparent to those skilled in the art, any other appropriate power supply may be used.
• the current preferably, must be distributed evenly amongst all cells (e.g., 16, 96) and the individual cell current l is calculated from the total current / t according to equation (1) (which is set out for a 16 well embodiment).
• Electrode surface modification As discussed, according to one embodiment of an apparatus of the invention, electrodes of the apparatus have immobilized redox catalysts at their surfaces. Polypyrrole film deposition via electropolymerization may be advantegeously used to attach catalysts to the electrode surfaces (Deronzier et al. (1996)) (see Figure 4(a)). Films of low adhesion are strengthened by copolymerization of pyrroles with monomers that are covalently attached to the oxidized surfaces (see Figure 4(b)). Catalyst precursors are immobilized at the anode or cathode, and are thereby transformed into transient redox-active species that will react with the corresponding substrates at the solid/liquid interface.
• a library of substituted pyrroles will be generated according to Figure 12.
• the length and nature of the spacer X is expected to influence conductivity and reagent permeability and constitutes a logical "point of diversity".
• a library of solid supports may be generated by anodic polymerization of the film precursor library on the electrode array of the SAEP.
• the electrode platform may be regenerated upon polishing off the polymeric electrode modifiers.
• the materials preferably possess the highest conductivity in both cathodic and anodic regions.
• Figure 14 summarizes an illustrative experiment. It involves the solid phase synthesis of a library of reverse-turn peptidomimetics (Leznoff (1978)). Two electrochemically controlled steps are mixed with traditional chemical reactions in this example: c. anodic oxidation; d. cathodic reduction.
• electrooxidative cyclization should provide the bicyclic lactam ring, whereas selective cleavage of the PP/PT-supported molecules will be based on the electroreductive scission of the sulfonamde bond (Pilard et al. (1998)).
• each well could contain the same substrate - its electrochemical transformation is followed spectroscopically. According to this protocol it will become possible to select electrode modification chemistry with optimal performance in a given chemical or electrochemical library synthesis.
• a Gilson 8x200 Pipetman may be used in small applications of the apparatus of the invention, however, to increase the throughput, a liquid handler (Gilson 215) for reaction layout, reagent dissolution and dispensing into J-KEM 96HC reaction blocks may be used. As will be appreciated, any liquid handler or reaction blocks may be used.
• the liquid-dispensing probe of the Gilson instrument has a liquid level sensing capability, essential to perform extractive work-ups.
• Solid phase extractions may be carried out using the 1ST VacMaster station and the Polyfiltronics hardware.
• a Gilson instrument may be integrated with Hewlett Packard 1100 LC/MS instrument or similar apparatus.
• the Savant DDA concentrator enables preparation of analytical samples and if necessary, allows for obtaining mass yields of individual library members.
• Examples 1-4 illustrate the ⁇ -alkoxylation of carbamates and sulfonamides (Nyberg et al. (1976); Edberson et al. (1979); Shono et la. (1984)).
• the process constitutes a direct and convenient method for generation and trapping of ⁇ -acyliminium cations.
• An alternative way of making the derivatized ⁇ -alkoxycarbamates is through the reduction of N- alkoxycarbonylactams (Nagasaka et la. (1986)). The latter method, however, requires cooling of the reaction mixture (-6°C) and relatively long reaction time (4 - 5 hours).
• the electrochemical method of the invention can essentially be performed at room temperature and typical reaction time is only 10 minutes for a reaction on a 1 mmol scale.
• the corresponding ⁇ - alkoxycarbamates are versatile synthetic intermediates and can be further elaborated into valuable products (Shono (1984)).
• the electrolyte solution in each cell contained the substrate (0.5 M), tetrabutylammonium tetrafluoroborate (Bu4N + BF4-) as supporting electrolyte (0.05 M), tetralin as a GC internal standard, and 1 :1 acetonitrile/alcohol as co-solvent in the case of substrate 1 - 5 (See Table 1 for compounds) or just acetonitrile in the case of substrate 6 - 11.
• the SAEP was submerged in a water bath to maintain temperature at 30°C. Electrolysis proceeded at constant current until theoretical charge (2.0 F) had been passed through each cell.
• SPE solid phase extraction
• the substrate 2 gave equal amounts of two diastereomeric products.
• the alkoxylation of sulfonamide 5 and intramolecular cyclization of substrates 6 - 11 that led to the isolation of a series of hetero-bicyclic compounds, have also been conducted and the yields are given in Table 1. These alkoxylated derivatives can be easily transformed into valuable amidoalkylation productions, as shown by Shono (Shono (1984)).
• the rate-limiting step in surface electrocatalysis is the reaction between immobilized catalysts and dissolved substrates (Anson (1980)).
• the efficiency of a given system therefore, largely depends on film porosity that modulates the mass transport in the diffusion layer. It is preferable to incorporate Keggin-type heteropolyanion salts (Girault et al. (1987)) within the film during electropolymerization. Subsequent washing of the surface leaves correspondingly sized domains (Aizawa et al. (1986)).
• Catalyst loadings are controlled by copolymerization of varied ratios of substituted and unsubstituted pyrroles. Preferably, optimization centers on the catalytic performance of the electrogenerated "combinatorial polymers" (Menger et al. (1995); Menger (1997)).
• Figure 10 illustrates the use of polypyrrole-based films for the catalytic reduction of oxygen to H 2 0, a process of great commercial value in the development of fuel cells.
• three pyrrole- containing monomers A, B, and C ( Figure 10) are anodically polymerized to give a film composed of randomly sequenced polymer chains. It is expected that, upon complexation of the Cu(l) and Co(ll) ions, certain segments of these polymers (e.g., the ACB unit) possess catalytic activity for the four electron reduction of oxygen to H 2 0, emulating the active site of cytochrome c (Collman et al. (1997)).
• polymeric transition metal catalysts for the non-thermal activation of CO 2 at atmospheric pressure may be developed.
• Recent studies have documented the use of homogeneous Ni and Cr catalysts for the formation of carbonates from epoxides and C0 2 (Tascedda et al. (1995); Kruper et al. (1995)).
• a cyclam-based surface the kinetic resolution of epoxides with cathodically activated C0 2 (see Figure 11 (b)) at potentials where reduction to CO is inhibited may be investigated.
• a cyclam ligand library may be derived from chiral tetraamine precursors, pyrrole-containing diesters, and 1st row transition metal salts.
• "assay" for the catalytic activity of a given film will follow the electropolymerization step.
• the apparatus of the present invention will enable the performance of parallel synthesis of film precursor libraries, electropolymerization of diverse monomers, characterization of the resulting films, and investigation of the films' catalytic activities in a variety of redox processes and has application in the following, non-limiting areas of chemistry:
• Electrodes Electrocatalytic Hydrogenolysis of N-0 and N-N Bonds.
• NAIkoxycarbonyllactams with NaBH4/EtOH-H+ A Facile Synthesis of a-Ethoxyurethanes. Heterocycles, 1986, 24(5), 1231-1232.
• Rapoport H. et al. J. Org. Chem. 1988, 53, 2367.

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