Process for preparing a self-supported chiral catalyst polymer and the so-obtained catalyst polymer

Abstract

The present invention refers to a process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization and the so-obtained catalyst polymer. The present invention discloses a new type of at least heterogeneous chiral catalysts which are easily accessible via a self-supported non-radical polymerization, utilizing a homogeneous chiral catalyst and optionally a homogeneous linker. These heterogeneous chiral materials can be used as catalysts for various chemical transformations.

Description

[0001] PROCESS FOR PREPARING A SELF-SUPPORTED CHIRAL CATALYST POLYMER AND THE SO-OBTAINED CATALYST POLYMER

[0002] The present invention refers to a process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization and the so-obtained catalyst polymer. The present invention discloses a new type of at least dimeric heterogeneous chiral catalysts which are easily accessible via a self-supported non-radical polymerization, utilizing a homogeneous chiral catalyst and optionally a homogeneous linker. These heterogeneous chiral materials can be used as catalysts for various chemical transformations.

[0003] Since the introduction of the concept of asymmetric organocatalysis over two decades ago, it has gained vast attention among chemists and hence rapidly developed. Based on the fundamental modes of activation (Lewis acid, Bronsted acid, Bronsted base and Lewis base) and its numerous applications in many diversified chemical transformations, it now became a main pillar in the field of asymmetric catalysis. Despite these catalyst developments and advancements, their application in a technical process is limited. One of the main reason for their limited use as a catalyst in an industrial process, is the homogeneous nature of these catalysts which requires additional steps for separation, and isolation for their reusability. Often, these operations are costly and potential loss of catalyst is also observed. To overcome the problem, heterogenization of homogeneous chiral organocatalysts has been attempted with moderate to good success in certain classes of catalysts.

[0004] In the prior art, reactions for building up polymer chains optionally having chiral building blocks are known.

[0005] For example, US 8 067 398 B2 discloses a process for preparing self-supported chiral polymer, and more precisely, a biodegradable chiral polymer.

[0006] Similarly, Bor et al. disclose (MACROMOLECULES (Vol. 26, no. 21 , 11 October 1993 (1993-10-11), pages 5664-5670) the preparation of a chiral polymer without any catalytic activity.

[0007] Itsuno Shinichi et al. disclose, in one Example only, (POLYMER CHEMISTRY, Vol. No 9 (2011-01-01), page 1942) the preparation of a chiral catalyst in the form of quaternary ammonium ionic salts. In JACS, Vol. 119, (1997-05-01), pages 4313-4314, Huang Wei-Sheng et al. describe a method for preparing a polymeric ligand for metal catalysis. Such ligand bound metal catalysis leads to metal leaching and thus, to the loss of catalytic activity of the metal catalyst.

[0008] Furthermore, several attempts for preparing supported catalysts have been published in the prior art. A reaction between a functionalized homogeneous chiral catalyst with a solid support such as a polystyrene polymer, textile, monolith etc. are disclosed in WO 2013- 178640 A1 , WO2015-086793 A1 and WO2017-08832A1.

[0009] The radical co-polymerization of a functionalized chiral homogeneous monomer with a homogeneous achiral monomer is described in Tetrahedron 64 (2008) 1316-1322 and in Advanced Synthesis & Catalysis 2010, 352, 281-287.

[0010] The oxidative, radical self-polymerization of a chiral homogeneous catalyst is disclosed in Advanced Synthesis & Catalysis 2011 , 353, 3101-3106, in Advanced Materials 2009, 21 , 702-705; and in Angew. Chem. Int. Ed. 2012, 51 , 5456-5459.

[0011] The insoluble porous polymerization of homogeneous chiral basic organocatalyst was disclosed in Chemical Communications 2010, 46, 970-972.

[0012] The said heterogeneous analogs of the known homogeneous catalysts have limited applications because of their specific type of activation mode which significantly reduces the scope of the chemical transformation.

[0013] Another major problem is their considerably reduced reactivity compared to their homogeneous ones. The reasons behind their low reactivity are a) the dead volume of these catalysts due to the introduction of the supporting materials (resign, textile etc.) b) limited available active catalytic species c) overall catalyst structure and porosity.

[0014] To overcome the reactivity and expanding the scope of various chemical transformations, the present invention provides a new strategy for the heterogenization of known and unknown chiral homogeneous catalysts. Therefore, the said heterogeneous materials are utilized for asymmetric Bronsted acid I Lewis acid catalysis and / or for asymmetric Bronsted base I Lewis base catalysis in various chemical transformations.

[0015] In more detail, the inventors have considered to start from a known or unknown catalyst building block, which contains the desired functional groups, and optionally a linker, which contains the desired functional groups.

[0016] For illustration purposes, the following schemes are used. In the inventive concept, the building block might comprise the following formulae and the reactions between the building blocks are schematically illustrated as follows:

[0017] Nu = nucleophile E = electrophile p > 1 n > 1 ; m > 1 where C = homogeneous chiral caralyst

[0018] E = electrophile Nu = nucleophile p > 1

[0019] E = electrophile Nu = nucleophile (Nu1— c Nu2) n m+

[0020] Nu = nucleophile E = electrophile p > 1 Nu1= Nu2; Nu1Nu2E1= E2; E1E2n > 1 ; m > 1 n > 1 ; m > 1 or

[0021] Nu = nucleophile E = electrophile Nu1= Nu2; Nu1Nu2E1= E2; E1E2n > 1 ; m > 1 n > 1 ; m > 1 p > 1

[0022] Utilizing said building blocks of the illustrated formula as a platforms molecules for the synthesis of self-supported heterogeneous catalysts presents the following advantages: a) The catalyst (C) is already known and readily functionalizable; b) The linker (L) is readily available and also functionalizable; c) All mentioned compounds are with limited dead volume and thus provide higher reactivity.

[0023] Thus, the present invention gives guidelines for a more efficient and general heterogenization platforms towards a broad range of chiral organocatalysts.

[0024] As illustrated schematically above, the present invention is directed to a process for preparing a polymer of Formula (III) comprising (-C-o-C-o- )nor an alternating polymer of Formula (IV) comprising (-C-o-L-o-)n. Though it is generally possible that a dimer of the reaction partners might act catalytically, it is preferred that step b) in the inventive process is repeated several times up to many hundred times so that a self-supported solid catalyst is prepared. In said polymer of Formula (III) or of Formula (IV), the unit -o- represent the bond or the group which results from the reaction of the said reaction pair which is selected from a nucleophilic group-electrophilic group-reaction pair or a diene-dienophile-reaction pair. In a simple form, the unit -o- might exemplarily result from the reaction of a nucleophilic group such as -OH on the catalyst molecule (C=Cat) HO-Cat-OH with an electrophilic group on the reaction partner molecule such as O=(OR)C-L-C(OR)=O, resulting in a group between catalyst (C=Cat) and linker such as HO-Cat-O-C(=O)-L-C(OR)=O and in a very simple form, the unit -o- might simply be an oxygen between catalyst and linker such as - Cat-O-L-. In more detail, the present invention is directed to a process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization, said process comprising the steps of: a) reacting a compound of Formula (I) (X1)n-C-(X2)mwith a compound selected from the group consisting of a compound of Formula (I) and a compound of Formula (II) (X1)n- L-(X2)m, whereby a dimer of the reacting compounds comprising at least one unit -o- is formed, and optionally b) reacting the product of step a) with a further compound selected from the group consisting of a compound of Formula (I) and a compound of Formula (II) whereby an oligomer of the reacting compounds comprising at least two units -o- is formed, and optionally, c) repeating step b) at least once, whereby an oligomer comprising one further unit -o- per step b) is formed, wherein C represents a chiral catalyst, L represents a hydrocarbon linker, X1and X2are the same or different and are chosen on the respective compounds of Formula (I) and Formula (II) to represent a reaction pair, wherein said reaction pair is selected from a nucleophilic group-electrophilic group-reaction pair or a diene-dienophile- reaction pair, wherein

[0025] -o- represents a unit in the oligomer chain formed by the reaction partner pair, wherein n and m independently represent integers > 1 , preferably from 1 to 8, more preferably 1 to 4, even more preferably 1 to 2, and wherein the number of C in the polymer chain represents 2 to 100.000.

[0026] As schematically illustrated above, the reaction partners of the reaction pair react with each other and form a polymer chain, either as a polymer chain of catalyst units or as a catalystlinker copolymer. One reaction partner pair is usually reacting thus forming the bond between the building blocks, but the respective building block might comprise more than one reaction partner of the same kind, for example several nucleophilic groups or several electrophilic groups, one or two of which is usually reacting with the reaction partner and thus leaving one or more unreacted groups on the building block.

[0027] It should be clear to the skilled chemist that, at the end of the reaction steps and particularly due to the number of reactive groups on the reaction partners, unreacted reaction partners X1and X2might be present on the polymer chain which do not negatively influence the catalytic properties of the self-supported chiral catalyst and might further react to non- reactive species. In another embodiment, the present invention is directed to a process for preparing a selfsupported chiral catalyst polymer via a non-radical polymerization, said process comprising the steps of: reacting a compound of Formula (I) (X1)n-C-(X2)mwith a compound of Formula (II) (X1)n-L- (X2)m, in an organic solvent in the presence of a base for a sufficient period of time whereby the reaction between the reacting compounds is completed, wherein C represents a chiral catalyst, L represents a hydrocarbon linker, X1and X2are the same or different and are chosen on the respective compounds of Formula (I) and Formula (II) to represent a reaction pair, wherein said reaction pair is selected from a nucleophilic group-electrophilic group-reaction pair or a diene-dienophile-reaction pair.

[0028] Said reaction is usually carried out in a solvent, preferably an organic solvent optionally in combination with water, in the presence of a base for a sufficient period of time to complete the polymerisation process which is usually achieved in ta time range of up to 96 hours, sometimes depending on the reactants also in shorter time ranges of up to 48 hours or even up to 24 hours.

[0029] In a preferred embodiment of the latter embodiment, the present invention is directed to a process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization, wherein reacting a compound of Formula (I) (X1)n-C-(X2)mwith a compound of Formula (II) (X1)n-L-(X2)mis made in a stoichiometric ratio of the compound of Formula (I) (X1)n-C-(X2)mto the compound of Formula (II) (X1)n-L-(X2)min the range of 1 :1 to 1 :10, preferably in the range of 1 :2 to 1 :6.

[0030] It should also be clear to the skilled chemist that, at the end of the reaction steps; a polymer is formed the size of which is hard to be calculated. In the course of the polymer formation, usually thousands of building blocks are bonded to each other and the reactions stops when reactive groups Xi and X2will not be reacting anymore. At the end of the reaction, a solid polymer is formed and can be used for catalyzing the desired reaction without any significant loss of the activity in hundreds of reaction cycle.

[0031] According to the invention, a catalyst molecule having more than two electrophilic groups such as three or four electrophilic groups might be reacted with another catalyst or a linker molecule having two nucleophilic groups, leading, in a first step, to a dimer having unreacted electrophilic groups which react, in a next step, with another catalyst or linker molecule. Thus, the present invention also comprises reacting said building block having more than one reactive group with the reaction partner having one or more reactive groups. In any case, the reaction partners of the reaction partner pair are present as substituents on the catalyst, preferably offside the catalytic center in order not to greatly influence the catalytic activity, or on the hydrocarbon linker, preferably on opposing hydrocarbon chain ends thereof.

[0032] Though it is generally possible that a dimer of the reaction partners might be used as a catalyst, it is preferred that step b) in the inventive process is repeated several times up to many hundred times so that a self-supported solid catalyst is prepared.

[0033] Thus, in the inventive process, the self-supported catalyst might comprise, in a simple form, a dimer of the catalyst building block or a heterodimer of the catalyst and of the linker which solubility and support capabilities depend on the kind of the building blocks and the substitution kind and degree. Depending on the kind of reaction partner pair, the reaction between the building blocks is a substitution reaction between a nucleophilic group and an electrophilic group or a cycloaddition, the latter forming a cyclic building block between the reaction partners. The products of both reaction pathways are covered by the representation of formulae (III) and (IV).

[0034] In an embodiment of the process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization of the present invention, X1 and X2 on the compound of Formula (I) are each one partner of the nucleophilic group-electrophilic group-reaction pair, and X1 and X2 on the compound of Formula (II) are each the corresponding partner of the nucleophilic group-electrophilic group-reaction pair, if a compound of the Formula (I) is reacted with a compound of the Formula (II) X1-L-X2, or

[0035] X1 on the compound of Formula (I) is one partner of the nucleophilic group-electrophilic group-reaction pair and X2 on the compound of Formula (I) is the corresponding partner of the nucleophilic group-electrophilic group-reaction pair if a compound of the Formula (I) X1- C-X2is reacted with another compound of the Formula (I) X1-C-X2.

[0036] In another embodiment of the inventive process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization, X1 and X2 on the compound of Formula (I) are each one partner of the diene-dienophile-reaction pair, and X1 and X2 on the compound of Formula (II) are each the corresponding partner of the diene-dienophile- reaction pair, if a compound of the Formula (I) is reacted with a compound of the Formula (II) X1-L-X2, or

[0037] X1 on the compound of Formula (I) is one partner of the diene-dienophile-reaction pair and X2 on the compound of Formula (I) is the corresponding partner of the diene-dienophile- reaction pair if a compound of the Formula (I) X1-C-X2is reacted with another compound of the Formula (I) X1-C-X2.

[0038] Though it is possible according to the invention that a polymer of Formula (III) comprising (-C-o-C-o- )nor an alternating polymer of Formula (IV) comprising (-C-o-L-o-)n.are formed in the inventive process, the polymers of Formula (IV) comprising (-C-o-L-o-)n. are of particular importance. Depending on the molar ratio of the compound of Formula (I) (X1)n- C-(X2)mto the compound of Formula (II) (X1)n-L-(X2)m, the formation of an oligomer or polymer comprising more L building blocks than Cat-in the polymer chain might be advantageous as the catalytic centers are more spaced apart and might catalyze the reaction without any steric influences. Thus, it might be preferable to have a stoichiometric ratio of the compound of Formula (I) (X1)n-C-(X2)mto the compound of Formula (II) (X1)n-L- (X2)min the range of 1 :1 to 1 :10 or more. In practice, a stoichiometric ratio of compound of Formula (I) (X1)n-C-(X2)mto compound of Formula (II) (X1)n-L-(X2)m, in the range of 1 :2 to 1 :6 leads to satisfactory results of the formed catalyst-linker-polymer in the catalytic reaction where such self-supported catalyst is used. In such case, the polymer chain will comprise catalytically active species C in the polymer chain being separated or spaced apart from the closest catalytically active species C by several linker units so that exemplarily a sequence such as ..-C-L-L-L-L-L-C-L-L-L-L-L-L-L-C-... will statistically be formed.

[0039] If in a case, the compound of Formula (I) (X1)n-C-(X2)mor the compound of Formula (II) (X1)n-L-(X2)mhas more than one or two Xi or X2 , the stoichiometric ratio might be in the same range as given before.

[0040] According to the invention, the catalyst compound (X1)n-C-(X2)mis preferably a phosphoramidimido-compound as represented by the general formula (VI) below, said compound of Formula (VI) bearing n (X1)nand m (X2)mgroups for building up the oligomer or polymer chain.

[0041] In an embodiment of the inventive process, the nucleophilic group is preferably selected from the group consisting of -OH, -SH, -NHR, -B(OR)2, -SiR3, -OSiR3, -NRSiR3, -MgT, - ZnT, -SnR3, -Li, -Na, -PR2, -CO2-, -CHZ2, -CHRZ, -CR=PR3, -C CH, -CR=CHR, - C(OSiR3)=CR2, -CR=C(OSiR3)(OR), -CR2=CHR-CR2-SiR3, -C N=O, -CR=NR=O where T represents a halogen, preferably Cl, Br, I, Z may be the same or different and represents an electron withdrawing group such as OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, - C(OR)=O, -NO2, -SO2R, or -CN and wherein R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-Cs- heterocycloalkyl hydrocarbon, a Ce to C2o aromatic hydrocarbon or partially arene- hydrogenated forms thereof, or a Cs to C19 heteroaromatic hydrocarbon and .

[0042] In an embodiment of the inventive process, the electrophilic group is preferably selected from the group consisting of H, F, Br, Cl, I, CN, NO2, -NR2, OTf, OTs, ONs, OMs, -CH=O, - CR=O, -C(OH)=O, -C(OR)=O, O=CR-O-RC=O, -C(CI)=O, -C(Br)=O, -C(F)=O, -C(NR2)=O, -N=C=O, -N=C=S, -N=C=N-R, -CR2Z where R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C3- heterocycloalkyl hydrocarbon, a C6to C2o aromatic hydrocarbon or partially arene- hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon and Z represents C2-C8-heterocycloalkyl hydrocarbon.

[0043] Preferably, the reaction pair of the nucleophilic group and of the electrophilic group is comprising at least one nucleophilic group selected from -OH, -SH, -NHR, -B(OR)2, or - CO2_and at least one electrophilic group selected from F, Br, Cl, I, or CN. The reaction can be promoted by using a base such as NaH, Na2CO3and the reaction may proceed until the reactive groups are consumed or a reaction will not take place anymore due to steric conditions.

[0044] In an embodiment of the inventive process, the diene is preferably a diene substituent - RC=CR-CR=CR2, where R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C8-heterocycloalkyl hydrocarbon, a C6to C2o aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon.

[0045] In an embodiment of the inventive process, the dienophile is preferably a dienophile substituent -CR=CR2, where R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C8-heterocycloalkyl hydrocarbon, a Ce to C2o aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon, where at least one R is bearing an electron withdrawing group selected from OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R, or -CN.

[0046] In an embodiment of the inventive process, the hydrocarbon linker L is preferably selected from the group consisting of Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, Ce to C20 aromatic hydrocarbons and partially arene- hydrogenated forms thereof, and C2 to C19 heteroaromatic hydrocarbons, in particular selected from Ci to C20 straight chain aliphatic hydrocarbons or Ce to C20 aromatic hydrocarbons bearing n and m, preferably 1 to 4, more preferred 1 or 2 Xi and X2 reactive groups, preferably -OH or -SH groups such as 4,4’-dihydroxybiphenyl or similar aromatic of aliphatic dihydroxy compounds.

[0047] In an embodiment of the inventive process, the catalyst C is a chiral phosphoramidimido- compound as represented by the general formula (V):

[0048] Wherein:

[0049] Y1and Y2, independently from each other, represent O or NRN,

[0050] W is selected from preferably hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, U or a cationic organic group, or a substituted silicon -SiRlRllRl", wherein R1, R" and R111are the same or different and each stands for hydrogen, halogen, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, C3-C8- heterocycloalkyl, a Ce to C20 aromatic hydrocarbon or a partially arene-hydrogenated form thereof, or C5 to C19 heteroaromatic hydrocarbons,

[0051] R1, R2, R3and R4are, independently from each other, the same or different and are each an aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon group, each optionally being further substituted by one or more heterosubstituents, aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon groups, whereby R1may be forming a ring system with any one of R2, R3or R4and the other two of R2, R3or R4may be forming a ring system with each other; and

[0052] RNis an electron withdrawing group, being the same or different on each N and is selected from: -alkyl, -CO-alkyl, -(CO)-O-alkyl, sulfinyl alkyl, sulfonyl alkyl, -(P=O)-dialkyl, wherein alkyl is a Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen, preferably F and / or Cl, substituent on the alkyl residue; aryl, -CO-aryl, -(CO)-O-aryl, sulfinyl aryl, sulfonyl aryl, -(P=O)-diaryl, wherein aryl is a Ce to Cis aromatic hydrocarbon, preferably having at least one halogen, preferably F and / or Cl, substituent on the aryl residue; heteroaryl, -CO-heteroaryl, -(CO)-O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, - (P=O)-di-heteroaryl, wherein heteroaryl is a C2 to C20 aromatic hydrocarbon, preferably having at least one halogen, preferably F and / or Cl, substituent on the heteroaryl residue; or a tautomeric or ionic form thereof.

[0053] In another embodiment of the inventive process, the catalyst C is a phosphoramidimido- compound as represented by the general formula (V) wherein (R1and R2) and (R3and R4) each form a ring structure which are the same or different and is derived from a bridged, optionally dimeric, aromatic structure selected from biphenyl optionally substituted, BINOL, TADDOL, VAPOL, SPINOL, 1 ,1 '-binaphthalene, 1 ,1 '-bianthracene, 1 ,1-biphenanthrene, or a partially arene-hydrogenated form of such aromatic ring structure including 8H-BINOL, each of said rings systems optionally being substituted by one or more substituents which are the same or different on each position and are each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, Ce to C20 aromatic hydrocarbons or partially arene-hydrogenated forms thereof, or C5 to C19 heteroaromatic hydrocarbons, wherein the ring structures formed by (R1and R2) and (R3and R4) are the same or different, and wherein Y1, Y2and W are as defined before, or a tautomeric or ionic form thereof.

[0054] According to the invention, the catalyst compound (X1)n-C-(X2)mis preferably a phosphoramidimido-compound as represented by the general formula (VI) below, said compound of Formula (VI) bearing n (X1) and m (X2) groups for building up the oligomer or polymer chain wherein Xi, X2, n and m have the meaning as given above.

[0055] In more detail for said embodiment of the inventive process, the catalyst C is a phosphoramidimido-compound as represented by the general formula (VI): wherein in said formula (IV), the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, a C6to C20 aromatic hydrocarbon or a partially arene-hydrogenated forms thereof, or C5 to C19 heteroaromatic hydrocarbons, and Y1, Y2and W are as defined above, or a tautomeric or ionic form thereof. Any substituent R may itself bear further substituenst such Ci to C20 optionally substituted aliphatic hydrocarbons, heterosubstituents, in particular halogens, and others.

[0056] In a particular embodiment of the inventive process, the nucleophilic group-electrophilic group-reaction pair is comprising at least one fluorinated - partly or fully - Ce to C20 aromatic hydrocarbon on side of the catalyst or linker and the reaction partner being a aliphatic diol or aromatic diol compound such as a bisphenol compound as the counterpart.

[0057] In yet another embodiment of the inventive process, the catalyst C is a phosphoramidimido- compound as represented by the general formula (VII): wherein the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, C6to C20 aromatic hydrocarbons and partially arene-hydrogenated forms, or C5 to C19 heteroaromatic hydrocarbons, Y1, Y2and W have the meaning as defined before, or a tautomeric or ionic form thereof. In a further embodiment of the inventive process, the catalyst C is selected from the group consisting of wherein in said formulae, the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, Ce to C20 aromatic hydrocarbons and partially arene-hydrogenated forms, or C5 to C19 heteroaromatic hydrocarbons and W is as defined before, or a tautomeric or ionic form thereof.

[0058] The present invention is also directed to the self-supported chiral catalyst polymer which is obtainable by any one of the processes as defined before, and the use thereof in organic synthesis.

[0059] The use of the inventive self-supported chiral catalyst polymer is preferably the use as a chiral catalyst in organic synthesis, wherein the synthetic reaction is selected from aldol reactions, vinylogous aldol reactions, Mukaiyama aldol reactions, vinylogous Mukaiyama aldol reactions, Mukaiyama-Michael reactions, Michael additions, Mannich reactions, TMSCN additions onto aldehydes and ketones onto imines, esterifications, etherifications, pinacol rearrangements, acetalizations, transacetalization, spiroacetalization and related reactions, cycloadditions, hydroaminations, hydroalkoxylation, hydrations, haloalkoxylation, haloamination, olefin activations in general including ene-reactions and Prins reactions, Friedel-Crafts reactions, epoxide openings, Ritter reactions, nucleophilic substitutions of alcohols, asymmetric ring openings, asymmetric reductions, transfer hydrogenations, alkyne additions, imine additions, Strecker reactions, allylations, propargylations, reductions, epoxidations, olefin metathesis, isomerizations, Diels-Alder reactions, hetero- Diels-Alder reactions, aminalizations, iminium catalysis and enamine catalysis.

[0060] In the inventive process, the choice of the solvent is not critical and depends on the reaction partners. The solvent may be an aprotic non-polar organic solvent selected from diethyl ether, aromatic solvents such as benzene, toluene, aliphatic hydrocarbon solvents having 5 to 8 carbon atoms, such as pentane, hexane, or mixtures thereof, or any other solvent such as DMSO, AMF, THF optionally in combination with water, acetonitrile and others which does not adversely affect the polymerization reaction. The reaction conditions are also not critical and the reaction is usually carried out at a temperature between 0 °C and 300 °C, preferably 10 °C to 150 °C, under ambient pressure and preferably under an inert gas atmosphere.

[0061] The inventive process for preparing a self-supported chiral catalyst polymer via a nonradical polymerization process preferably makes use of a base such as NaH, KH, CaH2, KOBut, LiHMDS, LDA, LiTMP, Mg(TMP)2, Zn(TMP)2, Ba(OH)2, K2CO3, NaOAc, Ag2CO3, Et3N, / Pr2NEt, K3PO4, DBU or a similar base depending on the reactions partners.

[0062] In the context of the present invention, the meanings are as defined below. A hydrocarbon is preferably selected from Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbons, C3-C8-heterocycloalkyl, Ce to C2o aromatic hydrocarbons and partially arene- hydrogenated forms, or C5 to C19 heteroaromatic hydrocarbons.

[0063] Said Ci-C2o alkyl preferably represents a straight or branched alkyl group having from 1 to 20 carbon atoms which may optionally be substituted by one or more electron withdrawing groups such as OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R, or -CN.

[0064] 5- to 19-membered heteroaromatic hydrocarbon or shortly heteroaryl represents a mono- or optionally bicyclic aromatic heterocycle (heteroaromatic) having a total of 5 to 10 ring atoms, which contains up to three ring heteroatoms from the series N, O and / or S and is linked via a ring carbon atom or optionally via a ring nitrogen atom. Examples are: Furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, indolyl, indazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyrazolo[3,4-b]pyridinyl.

[0065] A heteroatom or heterosubstituent as defined according to the invention can be selected from OH, halogen CN, NO2, NO, NCO, -NOS, -SON, SO3H, a monohalogenomethyl group, a dihalogenomethyl group, a trihalogenomethyl group, CF(CF3)2, SF5, aliphatic, aromatic, heteroaromatic, primary, secondary, tertiary amine or ammonium bound through N atom, - O-alkyl (alkoxy), -O-aryl, -O-heteroaryl -O-SiRs3,-S-S-Rs, -S-Rs, -S(O)-RS, -S(O)2-Rs, - COOH, -CO2-RS, -BRS2, -PRS2, -OPRS2, amide, bound through C or N atom, formyl group, - C(O)-RS, -COOM, where M is a metal such as Li, Na, K, Cs, Ag. Rsmay be, independently from each other, the same or different and is each an aliphatic, heteroaliphatic, aromatic or heteroaromatic group, each optionally being further substituted by one or more heterosubstituents, aliphatic, heteroaliphatic, aromatic or heteroaromatic groups; and / or optionally bridged by an -O- atom, represents a halogenide. Halogen in the context of the invention means fluorine, chlorine, bromine and iodine.

[0066] When a range of values is listed, it is intended to encompass each value and sub-range within the range. For example “C1-6” is intended to encompass, Ci , C2, C3, C4, C5, Ce, C1-6, C1-5, C1-4, C1-3, C1-2, C2-6, C2-5, C2-4, C2-3, C3-6, C3-5, C3-4, C4-6, C4-5, and Cs-6.

[0067] Preferred alkyl groups in the context of the present invention are straight-chain or branched alkyl groups having 1 to 6 carbon atoms. Exemplary and preferred are: Methyl, ethyl, n- propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, 1-ethyl-propyl, n-pentyl and n- hexyl.

[0068] Preferred cycloalkyl groups in the context of the present invention are cycloalkyl groups having 3 to 7 carbon atoms. Exemplary and preferred are: Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

[0069] Preferred cycloalkyloxy groups in the context of the present invention are cycloalkyloxy groups having 3 to 7 carbon atoms. Exemplary and preferred are: Cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and cycloheptyloxy.

[0070] Preferred di-C1-C4 alkylamino groups in the context of the present invention are the following di-C1-C4 alkylamino groups: N,N-dimethylamino, N,N-diethylamino, N-ethyl-N- methyhamino, N-methyl-N-n-propylamino, N-isopropyl-N-methyhamino, N-isopropyl-N- ethyl-amino, N-isopropyl-N-n-propyhamino, N,N-diisopropylamino, N-n-butyl-N- methylamino and N-tert. - butyl-N-methylamino.

[0071] “Aryl” refers to a radical of a monocyclic or polycyclic e.g., bicyclic or tricyclic) 4n+2 aromatic ring system e.g., having 6, 10, 14, 18, 22 pi electrons shared in a cyclic array) having 6-20 ring carbon atoms and zero heteroatoms provided in the aromatic ring system (“Ce-2o aryl”). In some embodiments, an aryl group has six ring carbon atoms (“Ce aryl”; e.g., phenyl). In some embodiments, an aryl group has ten ring carbon atoms (“C aryl”; e.g., naphthyl such as 1-naphthyl and 2-naphthyl). In some embodiments, an aryl group has fourteen ring carbon atoms (“C14 aryl”; e.g., anthracyl). “Aryl” also includes ring systems wherein the aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the radical or point of attachment is on the aryl ring, and in such instances, the number of carbon atoms continue to designate the number of carbon atoms in the aryl ring system. Unless otherwise specified, each instance of an aryl group is independently optionally substituted, i.e., unsubstituted (an “unsubstituted aryl”) or substituted (a “substituted aryl”) with one or more substituents. In certain embodiments, the aryl group is unsubstituted Ce-14 aryl. In certain embodiments, the aryl group is substituted Ce-14 aryl.

[0072] 6- to 20-membered aryl generally represents a mono-, bi- or tricyclic carbocyclic aromatic which in turn may bear from 0 to 5 substituents selected from the list: C1-C12-Alkyl, C1- C12-alkoxy, di-C1-C4-alkylamino, C3-C12-cycloalkyl, C3-C12-cycloalkyloxy, 6- to 18- membered aryl, 5- to 10-membered heteroaryl, halogen, cyano, nitro.

[0073] Preferred aryl groups in the context of the present invention are: Phenyl, naphthyl, anthryl, methylphenyl, dimethylphenyl, trimethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, pentafluorophenyl, perfluoronaphthyl; trifluoromethylphenyl, dimethylaminophenyl, C1-C12 alkoxycarbonylphenyl.

[0074] “Aralkyl” is a subset of alkyl and aryl and refers to an optionally substituted alkyl group substituted by an optionally substituted aryl group. In certain embodiments, the aralkyl is optionally substituted benzyl. In certain embodiments, the aralkyl is benzyl. In certain embodiments, the aralkyl is optionally substituted phenethyl. In certain embodiments, the aralkyl is phenethyl. 5- to 19-membered heteroaromatic hydrocarbon or shortly heteroaryl represents a mono- or optionally bicyclic aromatic heterocycle (heteroaromatic) having a total of 5 to 10 ring atoms, which contains up to three ring heteroatoms from the series N, O and / or S and is linked via a ring carbon atom or optionally via a ring nitrogen atom. Examples are: Furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, indolyl, indazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyrazolo[3,4-b]pyridinyl.

[0075] “Heteroaryl” refers to a radical of a 5-20 membered monocyclic or bicyclic 4n+2 aromatic ring system {e.g., having 6, 10, 14 or 18 pi electrons shared in a cyclic array) having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur (“5-14 membered heteroaryl”). In heteroaryl groups that contain one or more nitrogen atoms, the point of attachment can be a carbon or nitrogen atom, as valency permits. Heteroaryl bicyclic ring systems can include one or more heteroatoms in one or both rings. “Heteroaryl” includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups wherein the point of attachment is on the heteroaryl ring, and in such instances, the number of ring members continue to designate the number of ring members in the heteroaryl ring system. “Heteroaryl” also includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more aryl groups wherein the point of attachment is either on the aryl or heteroaryl ring, and in such instances, the number of ring members designates the number of ring members in the fused (aryl / heteroaryl) ring system. Bicyclic heteroaryl groups wherein one ring does not contain a heteroatom {e.g., indolyl, quinolinyl, carbazolyl, and the like) the point of attachment can be on either ring, i.e., either the ring bearing a heteroatom e.g., 2— indolyl) or the ring that does not contain a heteroatom {e.g., 5— indolyl).

[0076] 5- to 10-membered heteroaryl generally represents a mono- or optionally bicyclic aromatic heterocycle (heteroaromatic) having a total of 5 to 10 ring atoms, which contains up to three ring heteroatoms from the series N, O and / or S and is linked via a ring carbon atom or optionally via a ring nitrogen atom. Examples are: Furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, indolyl, indazolyl, quinolinyl, isoquinolinyl, naphthyridinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyrazolo[3,4- b]pyridinyl.

[0077] Exemplary 5-membered heteroaryl groups containing one heteroatom include, without limitation, pyrrolyl, furanyl and thiophenyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include, without limitation, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include, without limitation, triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include, without limitation, tetrazolyl. Exemplary 6-membered heteroaryl groups containing one heteroatom include, without limitation, pyridinyl. Exemplary 6-membered heteroaryl groups containing two heteroatoms include, without limitation, pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, without limitation, triazinyl and tetrazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include, without limitation, azepinyl, oxepinyl, and thiepinyl. Exemplary 5,6— bicyclic heteroaryl groups include, without limitation, indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzthiazolyl, benzisothiazolyl, benzthiadiazolyl, indolizinyl, and purinyl. Exemplary 6,6- bicyclic heteroaryl groups include, without limitation, naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.

[0078] “Heteroaralkyl” is a subset of alkyl and heteroaryl and refers to an optionally substituted alkyl group substituted by an optionally substituted heteroaryl group.

[0079] Preferred heteroaryl groups in the context of the present invention are mono- or optionally bicyclic 5- to 10-membered heteroaryl groups containing up to two heteroatoms from the series N, O and / or S. Particularly preferred are monocyclic 5- or 6-membered heteroaryl groups with up to two heteroatoms from the series N, O and / or S such as, for example, furyl, thienyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl.

[0080] The present invention is further illustrated by the attached schematic Figures and the Experimental Part. In the Figures, the Figure illustrate:

[0081] Figure 1 : Synthesis of self-supported I DP catalyst (Example 1)

[0082] Figure 2: Synthesis of self-supported / I DP catalyst (Example 3, 4, 6, 7, 8, 9, 10, 11, 13) Figure 3: Synthesis of self-supported IDPi catalyst (Example 16-26)

[0083] Figure 4: Synthesis of self-supported phosphoric acid catalyst (Example 27)

[0084] Figure 5: Synthesis of self-supported PADI catalyst (Example 28)

[0085] Figure 6: Results of recyclability experiments

[0086] Figure 7: Characterisation of the catalyst of Example 4

[0087] Experimental Part

[0088] Example 1 : Synthesis of self-supported IDP catalyst

[0089] A flame dried flask with magnetic stir bar was charged with (S,S)-IDP catalyst 4,4'- azanediylbis(2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine 4-oxide) (50 mg, 1 equiv.), 4,4'-Biphenol (21.9 mg, 2.1 equiv.), NaH (11.7 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (82% yield). This solid material was then used for catalysis without further purification.

[0090] Example 2: Synthesis of self-supported IDP catalyst

[0091] A flame dried flask with magnetic stir bar was charged with (S,S)-IDP catalyst 4,4'- azanediylbis(2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine 4-oxide) (500 mg, 1 equiv.), 4,4'-Biphenol (116 mg, 2.1 equiv.), K2CO3 (246 mg, 6 equiv.) and DMSO (5 mL). The mixture was stirred at 40 °C for 1 h, 85 °C for 2 h then 145 °C for 2 h. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (95% yield). This solid material was then used for catalysis without further purification.

[0092] Example 3: Synthesis of self-supported / IDP catalyst

[0093] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol— ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), 4,4'-Biphenol (21.3 mg, 2.1 equiv.), NaH (10.9 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (82% yield). This solid material was then used for catalysis without further purification.

[0094] Example 4a: Synthesis of self-supported / IDP catalyst

[0095] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (705 mg, 1 equiv.), 4,4'-Biphenol (152 mg, 2.1 equiv.), NaH (93 mg, 6 equiv.) and DMF (7 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (93% yield). This solid material was then used for catalysis without further purification.

[0096] Example 4b: Characterisation of the catalyst of Example 4a

[0097] The solid catalyst of Example 4a was characterized using traditional techniques for heterogeneous catalysts as illustrated in Figure 7.

[0098] The Powder XRD (A) showed that the synthesized catalyst is a non-crystalline material.

[0099] In Infrared Spectrum (B), the characteristic OH vibration peak (-3300 cm'1) is absent in / IDP catalyst (black). The heterogeneous catalyst has the expected OH peak (red). The peak in the fingerprint region at 820 cm'1is due to C-H bending of 1 ,4-disubstituted group. This is present in both heterogeneous catalyst and biphenol.

[0100] Thermogravimetric analysis (TGA) is performed (C) in the temperature range 35 to 800 °C at a ramp of 15 °C / min under argon atmosphere. After measurement, black material was obtained. No melting of the compound was observed. 10 wt% loss from 242 °C to 333 °C and from 570 °C 29 wt% weight loss.

[0101] Elemental Analysis (E) showed the following % (%C 62.21 , %H 2.39, %N 1.11 , %S 1.46, %P 2.49, %O 9.79.

[0102] Finally, the obtained solid catalyst was also characterized by TEM (D).

[0103] Example 5: Synthesis of self-supported / IDP catalyst

[0104] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , 1 '-biphenyl]-4,4'-diol— ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (49 mg, 1 equiv.), 4,4'-Biphenol (10 mg, 2.1 equiv.), K2CO3 (26 mg, 7 equiv.) and DMSO (1 mL). The mixture was stirred at 85 °C for 24 h. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (97% yield). This solid material was then used for catalysis without further purification.

[0105] Example 6: Synthesis of self-supported / 1DP catalyst

[0106] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), 2,6-Binaphthol (30.7 mg, 4 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light brown powder (56% yield). This solid material was then used for catalysis without further purification.

[0107] Example 7: Synthesis of self-supported / IDP catalyst

[0108] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol--perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), [1 , 1 '-biphenyl]-4,4'-dithiol (23.9, 4 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light brown powder (56% yield). This solid material was then used for catalysis without further purification.

[0109] Example 8: Synthesis of self-supported / IDP catalyst

[0110] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , 1 '-biphenyl]-4,4'-diol— ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), [1 , 1 '-biphenyl]-4,4'- dicarboxylic acid (26 mg, 4 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in white powder (31% yield). This solid material was then used for catalysis without further purification.

[0111] Example 9: Synthesis of self-supported / IDP catalyst

[0112] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), Bisphenol A (24.5 mg, 4 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in white powder (51% yield). This solid material was then used for catalysis without further purification.

[0113] Example 10: Synthesis of self-supported / IDP catalyst

[0114] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), 1 ,6-hexanediol (12.7 mg, 4 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in white powder (35% yield). This solid material was then used for catalysis without further purification.

[0115] Example 11 : Synthesis of self-supported / IDP catalyst

[0116] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , 1 '-biphenyl]-4,4'-diol— ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), Benzene-1 ,3,5-triol (6.7 mg, 2 equiv.), NaH (7.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in white powder (35% yield). This solid material was then used for catalysis without further purification.

[0117] Example 12: Synthesis of self-supported / IDP catalyst

[0118] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol--perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), 2,6-Dihydroxy-naphthalin (9.3 mg, 2.1 equiv.), K2CO3 (19 mg, 5 equiv.) and DMSO (1 mL). The mixture was stirred at 85 °C for 24 h. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (53% yield). This solid material was then used for catalysis without further purification.

[0119] Example 13: Synthesis of self-supported / IDP catalyst

[0120] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol--perfluoromethane (1 / 1 / 1 / 1)] (26.7 mg, 1 equiv.), 5,5',6,6'-Tetrahydroxy- 3,3,3',3'-tetramethyl-1 ,1'-spirobisindan (10 mg, 2 equiv.), K2CO3 (20.3 mg, 10 equiv.) and DMSO (1 mL). The mixture was stirred for 16 h at 85 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (32% yield). This solid material was then used for catalysis without further purification.

[0121] Example 14: Synthesis of self-supported / IDP catalyst

[0122] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , 1'-biphenyl]-4,4'-diol- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (48.79 mg, 1 equiv.), 4,4'-Biphenol (10 mg, 2.0 equiv.), Lithium hydroxide-Monohydrate (3.2 mg, 5 equiv.) and DMSO (1 mL). The mixture was stirred at rt for 24 h. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and during the washing with organic solvents, the solid was dissolved.

[0123] Example 15: Synthesis of self-supported / IDP catalyst

[0124] A flame dried flask with magnetic stir bar was charged with (S,S)- / 1DP catalyst [1 ,1 ,1- trifluoro-N-((2S)-4-((4-oxido-2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxa phosphepin-4-yl)amino)-2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1- d: 1 ',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)methanesulfonamide-[1 , T-biphenyl]-4,4'-diol-- ethane-1 ,2-diol-perfluoromethane (1 / 1 / 1 / 1)] (50 mg, 1 equiv.), 4,4'-Biphenol (20.5 mg, 4.0 equiv.), CS2CO3 (89.7 mg, 10 equiv.) and DMSO (1 mL). The mixture was stirred at rt for 24 h. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (53% yield). This solid material was then used for catalysis without further purification.

[0125] Example 16: Synthesis of self-supported IDPi catalyst

[0126] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- ((2S,2'S)-azanediylbis(2,6-bis(perfluoronaphthalen-2-yl)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1 ,1 ,1-trifluoromethanesulfonamide) (50 mg, 1 equiv.), 4,4'-Biphenol (18.9 mg, 4 equiv.), NaH (10.2 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (91 % yield). This solid material was then used for catalysis without further purification.

[0127] Example 17: Synthesis of self-supported IDPi catalyst

[0128] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-bis(4-(tert-butyl)phenyl)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1 ,3,4,5,6,7,8-heptafluoronaphthalene-2- sulfonamide) (300 mg, 1 equiv.), 4,4'-Biphenol (60.8 mg, 2.1 equiv.), NaH (39.2 mg, 6 equiv.) and DMF (3 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in yellow powder (86% yield). This solid material was then used for catalysis without further purification.

[0129] Example 18: Synthesis of self-supported IDPi catalyst

[0130] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-bis(4-(tert-butyl)phenyl)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide)-- [1 ,1'-biphenyl]-4,4'-diol--ethane-1 ,2-diol--perfluoromethane (1 / 1 / 1 / 1) (35 mg, 1 equiv.), 4,4'- Biphenol (4.4 mg, 1 equiv.), K2CO3 (16.2 mg, 5 equiv.) and DMSO (1 mL). The mixture was stirred for 48 h at 145 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (39% yield). This solid material was then used for catalysis without further purification.

[0131] Example 19: Synthesis of self-supported IDPi catalyst

[0132] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-di([1 , 1 '-biphenyl]-3-yl)-4l5-dinaphtho[2, 1 -d: 1 ',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1 ,3,4,5,6,7,8-heptafluoronaphthalene-2- sulfonamide) (100 mg, 1 equiv.), 4,4'-Biphenol (19.5 mg, 2.1 equiv.), NaH (10.5 mg, 5 equiv.) and DMF (1 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in yellow powder (89% yield). This solid material was then used for catalysis without further purification.

[0133] Example 20: Synthesis of self-supported IDPi catalyst

[0134] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-di(naphthalen-2-yl)-4l5-dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepine- 4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (35.2 mg, 1 equiv.), 4,4'- Biphenol (4 mg, 1 equiv.), K2CO3 (11.8 mg, 4 equiv.) and DMSO (1 mL). The mixture was stirred for 24 h at 145 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (72% yield). This solid material was then used for catalysis without further purification.

[0135] Example 21 : Synthesis of self-supported IDPi catalyst

[0136] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-di(benzofuran)-4l5-dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepine-4-yl- 4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (1 / 1 / 1 / 1) (50.5 mg, 1 equiv.), 4,4'- Biphenol (5.9 mg, 1 equiv.), K2CO3 (21.9 mg, 5 equiv.) and DMSO (1 mL). The mixture was stirred for 48 h at 150 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light yellow powder (53% yield). This solid material was then used for catalysis without further purification.

[0137] Example 22: Synthesis of self-supported IDPi catalyst

[0138] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-di(spiro[cyclopentane-1 ,9'-fluoren]-2'-yl)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(2,3,4,5,6-pentafluorobenzenesulfonamide) (50 mg, 1 equiv.), 4,4'-Biphenol (5 mg, 1.1 equiv.), K2CO3 (13.9 mg, 4 equiv.) and DMSO (1 mL). The mixture was stirred for 48 h at 145 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (69% yield). This solid material was then used for catalysis without further purification.

[0139] Example 23: Synthesis of self-supported IDPi catalyst

[0140] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N-(4-((2,6- bis(3-hydroxyphenyl)-4-(((trifluoromethyl)sulfonyl)imino)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepin-4-yl)amino)-2-(3-hydroxyphenyl)-6-(4-hydroxyphenyl)-4l5- dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)-1 ,1 ,1- trifluoromethanesulfonamide (55 mg, 1 equiv.), octafluoronaphthalene (37 mg, 4 equiv.), NaH (13.7 mg, 10 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in a soluble material which was suspended in pentane to obtain brown powder (11 % yield). This solid material was then used for catalysis without further purification. Example 24: Synthesis of self-supported IDPi catalyst

[0141] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-bis(3-bromophenyl)-4l5-dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepine- 4-yl-4-ylidene))bis(1 ,1 ,1 -trifluoromethanesulfonamide)--[1 , 1 '-biphenyl]-4,4'-diol--ethane- 1 ,2-diol--perfluoromethane (1 / 1 / 1 / 1) (50 mg, 1 equiv.), 4,4'-Biphenyldiboronic acid (31 mg, 4 equiv.), Pd(PPha)4 (3.7 mg, 0.1 equiv.), K2CO3 (26.6 mg, 6 equiv.) and THF-water (5:1 ; 1 mL & 0.2 mL). The mixture was stirred for 48 h at 80 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in light brown powder (77% yield). This solid material was then used for catalysis without further purification.

[0142] Example 25: Synthesis of self-supported IDPi catalyst

[0143] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N,N'- (azanediylbis(2,6-bis(6-bromonaphthalen-2-yl)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1 ,1 ,1-trifluoromethanesulfonamide) (50 mg, 1 equiv.), 4,4'-Biphenyldiboronic acid (27.8 mg, 4 equiv.), Pd(PPh3)4 (3.3 mg, 0.1 equiv.) K2CO3 (23.5 mg, 6 equiv.) and THF-water (5:1 ; 0.9 mL & 0.18 mL). The mixture was stirred for 48 h at 80 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et2O and Pentane) and dried, resulting in grey powder (50% yield). This solid material was then used for catalysis without further purification.

[0144] Example 26: Synthesis of self-supported IDPi catalyst

[0145] A flame dried flask with magnetic stir bar was charged with (S,S)-IDPi catalyst N-((4S)-4- (((4S)-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-9,14-bis(perfluoronaphthalen-2-yl)-4- (((trifluoromethyl)sulfonyl)imino)-4l5-dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepin-4- yl)amino)-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-9-(perfluoronaphthalen-2-yl)-4l5- dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepin-4-ylidene)-1 ,1 ,1- trifluoromethanesulfonamide-methane (1 / 2) (40 mg, 1 equiv.), 4,4'-Biphenol (4.4 mg, 1.5 equiv.), K2CO3 (10.8 mg, 5 equiv.) and DMSO (1 mL). The mixture was stirred for 2 h at 85 °C and then 3 h at 150 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (Et2O and Pentane) and dried, resulting in light brown powder (28% yield). This solid material was then used for catalysis without further purification. Example 27: Synthesis of self-supported Phosphoric acid catalyst

[0146] A flame dried flask with magnetic stir bar was charged with Phosphoric acid (2S)-4-hydroxy- 2,6-bis(perfluoronaphthalen-2-yl)dinaphtho[2,1-d:1',2'-f][1 ,3,2]dioxaphosphepine 4-oxide (50 mg, 1 equiv.), 4,4'-Biphenol (21.8 mg, 2 equiv.), NaH (11.7 mg, 5 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (63% yield). This solid material was then used for catalysis without further purification.

[0147] Example 28: Synthesis of self-supported PADI catalyst

[0148] A flame dried flask with magnetic stir bar was charged with PADI catalyst N-((2S)-2,6- bis(perfluoronaphthalen-2-yl)-4-(((trifluoromethyl)sulfonyl)imino)-4l5-dinaphtho[2,1-d:1',2'- f][1 ,3,2]dioxaphosphepin-4-yl)-1 ,1 ,1-trifluoromethanesulfonamide (50 mg, 1 equiv.), 4,4'- Biphenol (18.9 mg, 2. equiv.), NaH (10.2 mg, 5 equiv.) and DMF (0.5 mL). The mixture was stirred for 48 h at 25 °C. It was then cooled to 0 °C and quenched with aq. 10% HCI. The reaction mixture was filtered and the solid was washed with water followed by organic solvents (MeOH, EtOAc, Et20 and Pentane) and dried, resulting in light yellow powder (96% yield). This solid material was then used for catalysis without further purification.

[0149] Example 29: Cyclization of neral / citral to Isopiperitenol: (catalyst screening) catalyst (4-6 mg)

[0150] (5 mol%) toluene, -20 °C, 20 h

[0151] In an oven-dried vial with magnetic stir bar, catalyst was measured followed by addition of toluene (0.5 mL) and if desired cooled down to the desired reaction temperature. a,p- aldehyde (neral, 5.0 .L, 0.029 mmol, 1.0 equiv., Z:E-ratio >95:5 unless stated otherwise) was added in one portion and the reaction was stirred for 20 h. The reaction was quenched with triethylamine (10 pL) for homogeneous catalyst. Mesitylene was added as internal standard and the yield was determined by1H NMR spectroscopy. After evaporation of the solvent the crude mixture was purified by preparative TLC (silica gel, 10:1 hexane / EtOAc, v / v, partially stained with KMnCL) afforded Isopiperitenol as an inseparable mixture of diastereoisomers. The er and dr were determined by achiral and chiral GC.

[0152] Example 30: Recyclability Experiments:

[0153] In an oven-dried vial with magnetic stir bar, the catalyst of Example 4 was measured followed by addition of PhMe (0.5 mL) and cooled down to -20 °C. a,p- aldehyde (neral, 5.0 |iL, 0.029 mmol, 1.0 equiv., Z:E-ratio >95:5 unless stated otherwise) was added in one portion and the reaction was stirred for 20 h. Mesitylene was added as internal standard. The reaction mixture was then quickly centrifuged and solvent was decanted. The solids were then washed with PhMe (2x0.5 mL) and DCM (2x0.5 mL). After drying at high vacuum for 1 h, it was used for the next cycle. The analysis was performed as mentioned above.

[0154] Example 31 : Flow Reaction:

[0155] Immobilized / IDP 6.0 g

[0156] Flow rate = 5 mL min'1

[0157] In a flow reactor column was charged with 6 g solid catalyst of Example 4 and 30 g glass bead. A stock solution of neral in cyclopentyl methyl ether (CPME) was pass through the catalyst column at 10 °C with 5 mL min'1flow rate. This experimental setup resulted 55% conv. of neral to isopiperitenol in 50% yield with 98:2 er and >20:1 dr.

[0158] Example 32: Protolactonization: The solid catalyst in example 17 was used to evaluate its catalytic activity towards (-)- Boivinianin A synthesis via protolactonization strategy.

[0159] Example 17 catalyst

[0160] (5 mol%) toluene, 30 °C, 36 h

[0161] (-)-Boivinianin A

[0162] In an oven-dried vial with magnetic stir bar, catalyst was measured followed by addition of PhMe (0.25 mL) and carboxylic acid starting material (4.8 mg, 0.025 mmol, 1.0 equiv.). The reaction was stirred at 30 °C for 36 h. After that the reaction mixture was then quickly centrifuged and solvent was decanted. The solids were then washed with PhMe (2x0.5 mL). After drying at high vacuum for 1 h, it was used for the next cycle. The analysis was performed as mentioned above. After evaporation of the solvent the crude mixture was purified by preparative TLC (silica gel) and er was determined by chiral HPLC.

[0163] Example 33: Mukaiyama-Michael-Reaction:

[0164] The solid catalyst in example 17 was used to evaluate its catalytic activity towards Mukaiyama-Michael reaction.

[0165] In an oven-dried vial with magnetic stir bar, catalyst (0.025 equiv.) was measured followed by addition of PhMe (0.25 mL) and SKA (2.5 equiv.). The reaction mixture was stirred at 25 °C for 25 min. After that the reaction mixture was cooled at -80 °C and corresponding ketone (0.05 mmol, 1 equiv.) was added dropwise. The reaction was stirred at the same temperature for 16 h. After completion, 1 drop of Et3N was added to quench the reaction. The crude mixture was purified by preparative TLC (silica gel) and er was determined by chiral HPLC.

[0166] Example 34: Cationic Shifts of Aliphatic Hydrocarbons:

[0167] The solid catalyst in example 17 was used to evaluate its catalytic activity towards cationic shifts of aliphatic hydrocarbons. Ex n

[0168] In an oven-dried vial with magnetic stir bar, catalyst (0.05 equiv.) was measured followed by addition of n-hexane (0.25 M) and starting material (0.025 mmol, 1 .0 equiv.). The reaction was stirred at 25 °C for 5 days. The crude mixture was purified by preparative TLC (silica gel) and er was determined by chiral GC.

[0169] Example 35: Diels-Alder Reaction:

[0170] The solid catalyst in example 26 was used to evaluate its catalytic activity towards cationic shifts of aliphatic hydrocarbons.

[0171] In an oven-dried vial with magnetic stir bar, catalyst (0.025 equiv.) was measured followed by addition of PhMe (0.25 M) and allyl-TBS (0.025 mmol, 1.0 equiv.). The reaction mixture was stirred at 25 °C for 15 min. Then methyl cinnamate and cyclopentadiene were added. After 16 h, crude mixture was purified by preparative TLC (silica gel), er and dr were determined by chiral HPLC.

Claims

Claims1. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization, said process comprising the steps of: a) reacting a compound of Formula (I) (X1)n-C-(X2)mwith a compound selected from the group consisting of a compound of Formula (I) and a compound of Formula (II) (X1)n-L-(X2)m, whereby a dimer of the reacting compounds comprising at least one unit -o- is formed, and optionally b) reacting the product of step a) with a further compound selected from the group consisting of a compound of Formula (I) and a compound of Formula (II) whereby an oligomer of the reacting compounds comprising at least two units -o- is formed, and optionally, c) repeating step b) at least once, whereby an oligomer comprising one further unit -o- per step b) is formed, wherein C represents a chiral catalyst, L represents a hydrocarbon linker, X1and X2are the same or different and are chosen on the respective compounds of Formula (I) and Formula (II) to represent a reaction pair, wherein said reaction pair is selected from a nucleophilic group-electrophilic group-reaction pair or a diene-dienophile- reaction pair, wherein-o- represents a unit in the oligomer chain formed by the reaction partner pair, wherein n and m independently represent integers > 1 , preferably from 1 to 8, more preferably 1 to 4, even more preferably 1 to 2, and wherein the number of C in the polymer chain is preferably 2 to 100.000.

2. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization, said process comprising the steps of: reacting a compound of Formula (I) (X1)n-C-(X2)mwith a compound of Formula (II) (X1)n-L-(X2)m, in a solvent in the presence of a base for a sufficient period of time whereby the reaction between the reacting compounds is completed, wherein C represents a chiral catalyst, L represents a hydrocarbon linker, X1and X2are the same or different and are chosen on the respective compounds of Formula (I) and Formula (II) to represent a reaction pair, wherein said reaction pair is selected from a nucleophilic group-electrophilic group-reaction pair or a diene-dienophile- reaction pair.

3. Process according to claim 1 or 2, wherein reacting a compound of Formula (I) (X1)n- C-(X2)mwith a compound of Formula (II) (X1)n-L-(X2)mis made in a stoichiometric ratio of the compound of Formula (I) (X1)n-C-(X2)mto the compound of Formula (II) (X1)n-L- (X2)min the range of 1 :1 to 1 :10, preferably in the range of 1 :2 to 1 :6.

4. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of claims 1 to 3, wherein the nucleophilic group is selected from the group consisting of -OH, -SH, -NHR, -B(OR)2, -SiR3, -OSiR3, - NRSiR3, -MgT, -ZnT, -SnR3, -Li, -Na, -PR2, -CO2-, -CHZ2, -CHRZ, -CR=PR3, -C CH , -CR=CHR, -C(OSiR3)=CR2, -CR=C(OSiR3)(OR), -CR2=CHR-CR2-SiR3, -C N=O, - CR=NR=O where T represents a halogen, preferably Cl, Br, I, Z may be the same or different and represents OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, - C(OR)=O, -NO2, -SO2R, or -CN and wherein R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C8-heterocycloalkyl hydrocarbon, a Ce to C2o aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a Cs to C19 heteroaromatic hydrocarbon.

5. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of claims 1 to 4, wherein the electrophilic group is selected from the group consisting of H, F, Br, Cl, I, CN, NO2, -NR2, OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, O=CR-O-RC=O, -C(CI)=O, -C(Br)=O, - C(F)=O, -C(NR2)=O, -N=C=O, -N=C=S, _N=C=N-R, -CR2Z where R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C8-heterocycloalkyl hydrocarbon, a Ce to C2o aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon and Z C2-C8-heterocycloalkyl hydrocarbon.

6. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to claim 1 , wherein the diene is a diene substituent -RC=CR- CR=CR2, where R may be the same or different and represents H, a Ci to C2o straight chain, branched chain or cyclic aliphatic hydrocarbon, a C3-C8-heterocycloalkyl hydrocarbon, a Ce to C2o aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon.

7. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of claims 1 or 6, wherein the dienophile is a dienophile substituent -CR=CR2, where R may be the same or different and represents H, a Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon, a Cs-Cs-heterocycloalkyl hydrocarbon, a Ce to C20 aromatic hydrocarbon or partially arene-hydrogenated forms thereof, or a C5 to C19 heteroaromatic hydrocarbon where at least one R is bearing an electron withdrawing group selected from OTf, OTs, ONs, OMs, -CH=O, -CR=O, -C(OH)=O, -C(OR)=O, -NO2, -SO2R, or - CN .

8. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding claims, wherein the hydrocarbon linker L is selected from the group consisting of Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, C6to C20 aromatic hydrocarbons and partially arene-hydrogenated forms thereof, and C5 to C19 heteroaromatic hydrocarbons.

9. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a chiral phosphoramidimido-compound as represented by the general formula (V):Wherein:Y1and Y2, independently from each other, represent O or NRN,W is selected from preferably hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Al, Pb, La, Sm, Eu, Yb, U or a cationic organic group, or a substituted silicon -SiRlRllRl", wherein R1, R" and R111are the same or different and each stands for hydrogen, halogen, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, a C6to C20 aromatic hydrocarbon or a partially arene-hydrogenated form thereof, or C5 to C19 heteroaromatic hydrocarbons,R1, R2, R3and R4are, independently from each other, the same or different and are each an aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon group,each optionally being further substituted by one or more heterosubstituents, aliphatic, heteroaliphatic, aromatic or heteroaromatic hydrocarbon groups, whereby R1may be forming a ring system with any one of R2, R3or R4and the other two of R2, R3or R4may be forming a ring system with each other; andRNis an electron withdrawing group, being the same or different on each N and is selected from: i. -alkyl, -CO-alkyl, -(CO)-O-alkyl, sulfinyl alkyl, sulfonyl alkyl, -(P=O)-dialkyl, wherein alkyl is a Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbon having at least one halogen, preferably F and / or Cl, substituent on the alkyl residue; ii. aryl, -CO-aryl, -(CO)-O-aryl, sulfinyl aryl, sulfonyl aryl, -(P=O)-diaryl, wherein aryl is a C6to C18 aromatic hydrocarbon, preferably having at least one halogen, preferably F and / or Cl, substituent on the aryl residue; iii. heteroaryl, -CO-heteroaryl, -(CO)-O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, -(P=O)-di-heteroaryl, wherein heteroaryl is a C2 to C20 aromatic hydrocarbon, preferably having at least one halogen, preferably F and / or Cl, substituent on the heteroaryl residue; or a tautomeric or ionic form thereof.

10. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a phosphoramidimido-compound as represented by the general formula (V) wherein (R1and R2) and (R3and R4) each form a ring structure which are the same or different and is derived from a bridged, optionally dimeric, aromatic structure selected from biphenyl optionally substituted, BINOL, TADDOL, VAPOL, SPINOL, 1 ,1 '-binaphthalene, 1 ,1 '-bianthracene, 1 ,1-biphenanthrene, or a partially arene- hydrogenated form of such aromatic ring structure including 8H-BINOL, each of said rings systems optionally being substituted by one or more substituents which are the same or different on each position and are each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, C6to C20 aromatic hydrocarbons or partially arene-hydrogenated forms thereof, or C5 to C19 heteroaromatic hydrocarbons, wherein the ring structures formed by (R1and R2) and (R3and R4) are the same or different, and wherein Y1, Y2and W are as defined in claim 9,or a tautomeric or ionic form thereof.

11. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a phosphoramidimido-compound as represented by the general formula (VI):wherein in said formula (IV), the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, a Ce to C20 aromatic hydrocarbon or a partially arene-hydrogenated forms thereof, or C5 to C19 heteroaromatic hydrocarbons, and Y1, Y2and W are as defined in claim 9 , or a tautomeric or ionic form thereof.

12. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding claims, wherein the catalyst C is a phosphoramidimido-compound as represented by the general formula (VII):wherein the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, C6to C20 aromatic hydrocarbons and partially arene-hydrogenated forms, or C5 to C19 heteroaromatic hydrocarbons,Y1, Y2and W have the meaning as defined in claim 9, or a tautomeric or ionic form thereof.

13. Process for preparing a self-supported chiral catalyst polymer via a non-radical polymerization according to any one of the preceding, wherein the catalyst C is selected from the group consisting ofwherein in said formulae, the substituent R is the same or different on each position and is each selected from hydrogen, heterosubstituents, Ci to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, Cs-Cs-heterocycloalkyl, Ce to C20 aromatic hydrocarbons and partially arene-hydrogenated forms, or C5 to C19 heteroaromatic hydrocarbons and W is as defined in claim 9, or a tautomeric or ionic form thereof.

14. A self-supported chiral catalyst polymer obtainable by the process as claimed in any one of claims 1 to 13.

15. The use of a self-supported chiral catalyst polymer as claimed in claim 14 in organic synthesis.

16. The use of a self-supported chiral catalyst polymer as claimed in claim 15 as a chiral catalyst in organic synthesis, wherein the synthetic reaction is selected from aldol reactions, vinylogous aldol reactions, Mukaiyama aldol reactions, vinylogous Mukaiyama aldol reactions, Mukaiyama-Michael reactions, Michael additions, Mannich reactions, TMSCN additions onto aldehydes and ketones onto imines, esterifications, etherifications, pinacol rearrangements, acetalizations, transacetalization, spiroacetalization and related reactions, cycloadditions,hydroaminations, hydroalkoxylation, hydrations, haloalkoxylation, haloamination, olefin activations in general including ene-reactions and Prins reactions, Friedel- Crafts reactions, epoxide openings, Ritter reactions, nucleophilic substitutions of alcohols, asymmetric ring openings, asymmetric reductions, transfer hydrogenations, alkyne additions, imine additions, Strecker reactions, allylations, propargylations, reductions, epoxidations, olefin metathesis, isomerizations, Diels-Alder reactions, hetero-Diels-Alder reactions, aminalizations, iminium catalysis and enamine catalysis.

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