Process for the removal and return of a catalyst to a liquid phase medium

Abstract

A process for the selective removal of a component from a liquid phase and subsequently returning the component to a liquid phase is disclosed. A novel compound of formula I [SUP]-[[L]-[G]] a (I) in which L is a linking group, G is an aryl group having a leaving group LG selected from Cl, Br, I, sulfonate such as triflate, a diazo group, a nitrile, an ester and an alkoxy group and substituent Q is selected from H, NR 2 , OR, CO 2 R, F, Cl, NO 2 CN and SUP is a support having a plurality of groups -[L]-[G] bound to the support is contacted with the liquid phase to bind the component to the compound I thereby forming a captured component which is separated from and may be returned to the liquid phase. The compound I is especially useful in binding homogeneous catalysts to remove it from a reaction medium and selectively returning the catalyst to the reaction medium at a later stage. The compound is particularly useful for cross-coupling reactions, for example in Suzuki reactions.

1 - 4 . (canceled) 
     
     
         5 . A compound of formula I:
   [SUP][[L]-[G]] n   (I)
   wherein:
 L is a group linking G to SUP— and is selected from the group consisting of: 
 i) —(CH 2 ) h S(O) d [Y] m    
 ii) ((CH 2 ) n Y(CH 2 ) n ) m ; and 
 iii) —(CH 2 ) h [S(O) d ] m (CHD) n Z m  where D is selected from the group consisting of H, CN, OH, —C(O)OR, —C(O)NR 2 —C(O)OG, and —CONRG and at least one of S, D, and Z are present; and 
 wherein Y is independently selected from the group consisting of O, NR, S(O) d , CO, CO 2 , —NRCOZ m —, —Z m CONR—, —C═N—, and a heterocyclic ring where Z is independently O, S, NR; 
 d is independently 0 to 2, h is from 1 to 15, m is independently 0 or 1 and n is independently 0 to 4 and R is independently selected from H or a 01-12 alkyl group and a phenyl group; 
 G is selected from the group consisting of an alkyl group, an aryl group, a heterocyclic group and a heteroaryl group wherein the group G has: 
 i) leaving group LG selected from the group consisting of Cl, Br, I and a pseudohalide and 
 ii) substituent Q selected from the group consisting of H, NR 2 , N+R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , —CONR 2 , —NRC(O)R, F, Cl, NO 2 , CN and a ring formed between group Q and a part of group L; and 
 SUP is a silica support having a plurality n of groups -[L]-[G] bound to the support. 
   
     
     
         6 . The compound according to  claim 5  wherein the compound of formula I is of formula VI:
   [(O 3/2 )Si[L]G] a [Si(O 4/2 )] b [Si(O 3/2 )V′] c   (VI)
 
 wherein:
 V″ is an optionally substituted C 1-12 -alkyl, C 2-12 -alkenyl or C 2-12 -alkynyl group or an aryl group or C 1-12 -alkylaryl sulfide, sulfoxide, sulfone, amine or a polyalkyl amine or phosphine or other phosphorous containing group; 
 the free valences of the silicate oxygen atoms are saturated by one or more groups selected from: 
 silicon atoms of other groups of Formula VI; 
 hydrogen; 
 a linear or branched C 1-12 -alkyl group; 
 an end group of formula R 8   3 M 1 O 1/2 , a cross-linking bridge member or a polymer chains of formula R 8   q M 1 (OR 9 ) j O k/2  or Al(OR 9 ) 3-p O p/2  or R 8 Al(OR 9 ) 2-r O r/2  where M 1  is Si or Ti; 
 
 R 8  and R 9  are independently selected from a linear or branched C 1-40  alkyl group an aryl group and a C 1-40 -alkylaryl group; k is an integer from 1 to 3, q is an integer from 1 to 2 and j is an integer from 0 to 2 such that j+k+q=4; p is an integer from 1 to 3; and r is an integer from 1 to 2; and
 other known oxo metal bridging systems where the metal is zirconium, boron, magnesium, iron, nickel or a lanthanide; and 
 a, b and c are integers, a is greater than 0 and a, b and c are such that when b is 0 the ratio of a:c is from 0.001 to 1000 and when b is 1 or more the ratio of a:b is from 0.001 to 1000. 
 
 
     
     
         7 . The compound according to  claim 5  wherein L is a divalent group linking G to (O 3/2 )Si— and is selected from:
 i) —(CH 2 ) h  S(O) d [Y] m ; and 
 ii) (CH 2 ) n (Y) m (CH 2 ) h , where Y is selected from —CO 2 —, —CON(R)—, -and —N(R)CO—, h is independently 0 to 4, m is independently 0 or 1, n is independently 0 to 4 and d is from 0 to 2, and R is independently H, C 1-6  or phenyl. 
 
     
     
         8 . The compound according to  claim 5  in which the linking group L has a chain of at least three atoms and not more than 15 atoms between the silica group and group G. 
     
     
         9 . The compound according to  claim 5  in which linker group L is selected from:
 —(CH 2 ) 3 — 
 —CH 2 CH 2 CHC((O)OCH 3 )— 
 —CH 2 CH 2 CH(CN)— 
 —(CH 2 ) 2-3 NHCO— 
 —(CH 2 ) 2-3 CONH— 
 —(CH 2 ) 3 NHCH 2 — 
 —CH 2 CH 2 S— 
 —CH 2 CH 2 S(CH 2 ) 1-4 SCH 2 — 
 —CH 2 CH 2 S(CH 2 ) 1-4 NHCO— 
 
     
     
         10 . The compound according to  claim 5  in which leaving group LG is selected from a halide, a sulfonate, diazo group, nitrile, an ester and an alkoxy group. 
     
     
         11 . The compound according to  claim 5  in which substituent Q of group G is selected from H, NR 2 , N + R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , CONR 2  NRC(O)R, F, Cl, NO 2 , CN and a ring formed between group Q and a part of group L. 
     
     
         12 . The compound according to  claim 5  wherein the group G comprises an optionally substituted bromophenyl moiety or an optionally substituted bromoheteroaryl moiety. 
     
     
         13 . The compound according to  claim 5  wherein G comprises an aryl or heteroaryl group and substituent Q is located at the ortho or meta position relative to linker group L. 
     
     
         14 . The compound according to  claim 13  wherein Q is selected from H, NR 2 , N + R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , CONR 2  NRC(O)R, F, Cl, NO 2 , CN and a ring formed between group Q and a part of group L. wherein R is C1-6 alkyl. 
     
     
         15 . The compound according to  claim 5  wherein G comprises a heteroaryl group selected from: 
       
         
           
           
               
               
           
         
         and a heterocyclic group selected from 
       
       
         
           
           
               
               
           
         
         wherein J and K are independently selected from, when divalent, O, NR, S and CH 2  or, when trivalent, ═N—, ═CH— and wherein HET signifies a heteroatom-containing species being present within the ring encircling HET. 
       
     
     
         16 . The compound according to  claim 5  in which the linker group L is —[CH 2 CH 2 S(O) 0-2 ] 0-1  [CH 2 ] 0-3 [A″] 0-1 - where A″ is selected from the group consisting of:
 —NH(CO)—, 
 —N(CH 3 )— and —O(CO) 0-1 —. 
 
     
     
         17 - 19 . (canceled) 
     
     
         20 . An organometallic species comprising a catalyst CAT and compound of formula I according to  claim 5  wherein the catalyst CAT comprises a metal with or without ancillary ligands. 
     
     
         21 . An organometallic species according to  claim 20  of formula VII
   [SUP]-L-G-CAT-LG  (VII)
 
 wherein SUP, L, G and LG are as defined in  claim 5 . 
 
     
     
         22 . An organometallic species according to  claim 20  wherein the catalyst CAT comprises palladium, platinum, rhodium, iridium, ruthenium, copper, nickel or iron, optionally comprising an ancillary ligand. 
     
     
         23 . A homogeneously catalyzed process for the formation of a covalent bond between a carbon atom and a second carbon atom or a heteroatom in a reaction medium comprising a catalyst wherein the catalyst is selectively removed and returned to the reaction medium, the process comprising contacting a catalyst CAT wherein the catalyst CAT comprises a metal with or without ancillary ligands with a compound of formula II:
   R″-LG  (II)
   to produce an organometallic species of formula III:
   R″-CAT-LG  (III);
 
   treating the species of formula III with a compound of formula IV
   R″″[MET] e [X″] f   (IV)
 
   to replace the -leaving group LG with a group R″″ to form a compound of formula VIII
   R″-R″″  (VIII)
 
   and release the catalyst CAT into the reaction medium; contacting the catalyst with a compound of formula I or formula VI as defined in  claim 5  to remove the catalyst from the reaction medium; treating the catalyst by contacting with a compound of formula IV to return it to the reaction medium; and contacting the returned metal catalyst with a further feedstock to effect a further reaction to produce a second reaction product wherein:
 i) R″ and R″″ are independently selected from aryl, heteroaryl, benzyl, alkyl, vinyl, allyl, alkynyl, acyl, sulfonyl or a heterocyclic moiety; 
 ii) LG is a leaving group selected from halogen, pseudohalogen and OH; 
 iii) [MET] is selected from a metal capable of use in an organometallic species, and boron; 
 iv) X″ is selected from halogen and OH; 
 v) e is 0 or 1 and f is an integer from 1 to 4 selected to satisfy the free valencies of species R″″[MET] e -. 
   
     
     
         24 - 27 . (canceled) 
     
     
         28 . A compound of formula:
   [SUP]-[G] n′   (IA)
   wherein G is linked directly to SUP;   G is selected from an alkyl group, an aryl group, a heterocyclic group and a heteroaryl group wherein the group G has:
 i) a leaving group LG selected from Cl, Br, I and a pseudohalide; and 
 ii) substituent Q selected from NR 2 , N + R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , —CONR 2 —NRC(O)R, F, Cl, NO 2 , and CN; and 
   
       SUP is a silica support having a plurality n′ of groups [L]-[G] bound to the support. 
     
     
         29 . The compound according to  claim 28  in which leaving group LG is selected from a halide, a sulfonate, diazo group, nitrile, an ester and an alkoxy group. 
     
     
         30 . The compound according to  claim 28  in which substituent Q of group G is selected from H, NR 2 , N + R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , CONR 2  NRC(O)R, F, Cl, NO 2 , CN and a ring formed between group Q and a part of group L. 
     
     
         32 . The compound according to  claim 28  wherein the group G comprises an optionally substituted bromophenyl moiety or an optionally substituted bromoheteroaryl moiety. 
     
     
         32 . The compound according to  claim 28  wherein G comprises an aryl or heteroaryl group and substituent Q is located at the ortho or meta position relative to linker group L. 
     
     
         33 . The compound according to  claim 32  wherein Q is selected from H, NR 2 , N+R 3 , —N(R)CO 2 H, —N═CR 2 , OR, —O + (R)SiR 3 , CO 2 R, CO 2   − , CONR 2  NRC(O)R, F, Cl, NO 2 , CN and a ring formed between group Q and a part of group L, wherein R is C1-6 alkyl. 
     
     
         34 . The compound according to  claim 28  wherein G comprises a heteroaryl group selected from: 
       
         
           
           
               
               
           
         
         and a heterocyclic group selected from 
       
       
         
           
           
               
               
           
         
         wherein J and K are independently selected from, when divalent, O, NR, S and CH 2  or, when trivalent, ═N—, ═CH— and wherein HET signifies a heteroatom-containing species being present within the ring encircling HET. 
       
     
     
         35 . An organometallic species comprising a catalyst CAT and a compound of formula IA as defined in  claim 28  wherein the catalyst CAT comprises a metal with or without ancillary ligands. 
     
     
         36 . An organometallic species according to  claim 35  of formula VII
   [SUP]-G-CAT-LG  (VII)
 
 wherein SUP, G and LG are as defined in  claim 28 . 
 
     
     
         37 . An organometallic species according to  claim 35  wherein the catalyst CAT comprises palladium, platinum, rhodium, iridium, ruthenium, copper, nickel or iron, optionally comprising an ancillary ligand. 
     
     
         38 . A homogeneously catalyzed process for the formation of a covalent bond between a carbon atom and a second carbon atom or a heteroatom in a reaction medium comprising a catalyst wherein the catalyst is selectively removed and returned to the reaction medium, the process comprising contacting a catalyst CAT wherein the catalyst CAT comprises a metal with or without ancillary ligands with a compound of formula II:
   R″-LG  (II)
   to produce an organometallic species of formula III:
   R″-CAT-LG  (III);
 
   treating the species of formula III with a compound of formula IV
   R″″[MET] e [X″] f   (IV)
 
   to replace the -leaving group LG with a group R“ ” to form a compound of formula VIII
   R″-R″″  (VIII)
 
   and release the catalyst CAT into the reaction medium; contacting the catalyst with a compound of formula I or formula VI as defined in  claim 28  to remove the catalyst from the reaction medium;   treating the catalyst by contacting with a compound of formula IV to return it to the reaction medium; and contacting the returned metal catalyst with a further feedstock to effect a further reaction to produce a second reaction product wherein:
 i) R″ and R″″ are independently selected from aryl, heteroaryl, benzyl, alkyl, vinyl, allyl, alkynyl, acyl, sulfonyl or a heterocyclic moiety; 
 ii) LG is a leaving group selected from halogen, pseudohalogen and OH; 
 iii) [MET] is selected from a metal capable of use in an organometallic species, and boron; 
 iv) X″ is selected from halogen and OH; 
 v) e is 0 or 1 and f is an integer from 1 to 4 selected to satisfy the free valencies of species R″″[MET] e -.