Chapter Chapter – Palladium Catalyzed C-C bond Formation Involving Organoboronic Acids 5.1 Introduction Great effort has been made in the development of catalytic methods for C-C bond formations to synthesize many significant drugs, materials, optical devices etc.126 Owing to the low toxicity as well as high air and moisture stability, organoboronic acids have found a broad range of applications in synthetic chemistry.127 They are mostly used in cross coupling reactions to form biaryl units which are common in natural products.128 Recently, other applications in C-C bond forming processes such as 1,4-additions to unsaturated compounds, 1,2-additions to carbonyl compounds and oxidative aminations have also been reported.129 The aim here is to apply the palladium precursors and the hemilabile ligands described in chapter as catalysts for the Suzuki-Miyaura cross coupling reactions, 1,2- additions to aldehydes and 1,4-conjugate additions to α,βunsaturated ketones 5.1.1 Palladium catalyzed Suzuki-Miyaura cross coupling reactions Palladium-catalyzed Suzuki-Miyaura cross-coupling between organoboranes and organoelectrophiles has become one of the most important C-C bond formation methodologies (Equation 5.1).128 It enables facile syntheses of biaryls and alkylaromatics that are intermediates of pharmaceuticals, natural products and stereoselective reactions etc.130 For example, tetra-ortho-substituted biaryls can be prepared from this method with the use of bulky phosphines,131 hybrid ligands,132 and carbene complexes133 (Scheme 5.1 and 5.2) etc There are however some drawbacks, such as the cost of boron reagents, need for high temperatures and high Pd loadings (2-12 mol%) etc These have restricted the use of 93 Chapter asymmetric Suzuki cross-coupling reactions in producing biologically active biaryls134 and prompted the development of more efficient catalytic systems especially on ligand innovations Therefore, part of our research focus is to develop an efficient ligand/Pd catalyst system for coupling sterically hindered substrates and preferably, to extend further for asymmetric Suzuki-Miyaura cross-coupling reactions R1 R2 + X B(OH)2 catalyst R2 R1 Equation 5.1 A typical Suzuki-Miyaura cross coupling reaction.129 Br B(OH) + Base, Solvent 50-75oC R NMe2 PR' Fe R = Me, R' = Ph, , mol% Pd2(dba)3.CHCl3 used, 72 h, Product Yield = 85% R = Me, R' = Ph, mol% PdCl3 used, 144 h, Product Yield = 58% R = Ph, R' = Ph, mol% Pd2(dba)3.CHCl3 used, 72 h, Product Yield = 62% R = Me, R' = 4-Ph-CF3, mol% Pd2(dba) 3.CHCl used, 72 h, Product Yield = 66% 55 Ar P(t-Bu)2 PCy Fe Pd2(dba)3 Ar Fe Ar = Phenanthrenyl, mol% Pd used, 24 h, Product Yield = 65% Pd2(dba)3 Ar Ar 133 Ar Ar 134 Ar = Ph, 10 mol% Pd used, 25h, Product Yield = 25% DPPF/Pd2(dba) 3, 10mol% Pd used, 96 h, Product Yield = 95% Scheme 5.1 Reported Pd systems used to catalyze Suzuki – Miyaura cross couplings of hindered Suzuki naphthalene substrates.131a-b,132b 94 Chapter X B(OH)2 base solvent + 100 - 110oC 12-18h O O PCy2 OMe MeO N OTf 135 X = Br, mol% Pd2(dba)3 used, Product Yield = 85% + N - iPent Ar N N AriPent Cl Pd Cl 136 X = Br, mol% Pd(OAc)2 used, Product Yield = 91% X = Cl, mol% Pd(OAc)2 used, Product Yield = 71 - 96% 137 X = Br, Cat loading = 2mol%, Product Yield = 88% Scheme 5.2 Successful palladium catalytic Suzuki-Miyaura systems reported to be capable of producing biaryls with four ortho alkyl substituents.132a,133 5.1.2 Palladium catalyzed 1,2- addition of organoboronic acids to aldehydes Chiral diaryl methanols are important intermediates for the synthesis of medically active compounds (Figure 5.1).135 Generally, they can be obtained either by reduction of the corresponding unsymmetrical diaryl ketones or enantioselective aryl transfer reactions to aldehydes (1,2-addition reactions) (Scheme 5.3).136 However, both methods have severe limitations and only work well for a limited range of substrates It is accordingly pertinent a need to develop alternative pathways that can be applied to wider variety of carbinol derivatives 95 Chapter H H OH O X OH NMe2 neobenodine (used as drugs with antihistamine, anticholinergic, local-anaesthetic and laxative activties) X = O, NSO2CH3 2-Benzofuranylcarbinols (display antifungal and aromatic inhibiting activites) Figure 5.1 Some examples of diaryl methanols as intermediates for the synthesis of medically active compounds.135 O catalyst [H] OH * R' R catalyst R"2Zn O R Y H R R' Y = organoboron, organosilane, organozinc, organostanne, organomagnesium groups Scheme 5.3 General Synthetic routes to obtain biaryl methanols.136 The 1,2-addition to aldehydes has been investigated with a variety of protocols employing organoboron,129c,137 organozinc,138 organotin139 and organosilane140 compounds Among the catalytic methodologies used, the rhodium catalyzed 1,2-addition of arylboronic acids to aldehydes is especially notable 137a-b,f, 141 It would also be desirable to use cheaper metals Promising palladium catalysts such those of phosphapalladacycle,137c anionic palladacycles137i and thioether-imidazolinium137k that are active towards the 1,2-addition 96 Chapter reactions have accordingly emerged (Figure 5.2) On the other hand, use of palladium complexes with hybrid ligands towards catalytic additions of arylboronic acids to aldehydes is not known It is therefore of our interest to investigate the efficacy of our Pd/[P, N] ligands system towards 1,2-addition of arylboronic acids to aldehydes Ph2 P Pd Br PPh2 Fe Pd OAc 139 138 i-Pr Cl N i-Pr N [Pd(allyl)Cl]2 PhS 140 Figure 5.2 Phosphapalladacyclic complex (138), anionic palladacycle (139) and thioether-imidazolinium chloride (140)/[Pd(allyl)Cl]2 for the palladium catalyzed 1,2addition of arylborons to carbon-heteroatom double bonds.137c,i,k 5.1.3 Palladium catalyzed 1,4- conjugate additions of organoboronic acids to α,βunsaturated ketones Some of the enantiomerically enriched compounds possessing a chiral diarylmethane unit are known to be biologically active in antimuscarinics,142 antidepressants,143 and endothelin antagonists,144 and have received growing attention for their syntheses One of the straightforward methods is via conjugate addition of an aryl nucleophile to electron97 Chapter deficient olefins substituted with another aryl groups at the β position The 1,4-addition of arylboronic acids to enones and related substrates is a versatile method reported.137f,141c Although the catalysts reported are dominated by rhodium-based complexes,129c,140c,145 palladium(0)-SbCl3 (cat A),146 palladium-bipyridine (cat B),147 cationic palladium(II) complex (cat C)137g-h and palladacycles (cat D and E)148,137i have been reported as active catalysts for 1,4-addition reactions of arylboronic acids with α,β-unsaturated ketones and α-ketoesters (Scheme 5.4) Despite the ready availability of the reagents, the conjugate addition of arylboronic acids to activated ketones has been elusive until now Therefore, it is of interest to explore the potential application of the mixed donor hybrid ligands in the palladium-catalyzed 1,4 addition reaction of arylboronic acids to these ketones as well Ar O R O ArB(OH)2 catalyst R' R R' Catalyst: 10mol%Pd(OAc) 10mol% SbCl3 N 5mol% Pd(OAc)2 N cat B cat A O cat D dppe = Ph2P cat C PPh2 PR2 Pd 5mol% 5mol% [Pd(dppe)(PhCN) 2](SbF6)2 PPh2 Cl 5mol% Fe Pd OAc cat E Scheme 5.4 Reported active catalysts for 1,4-addition reactions of arylboronic acids with α,β-unsaturated ketones and α-ketoesters.137g-i, 146-148 98 Chapter 5.2 Results and discussion 5.2.1 Catalytic Studies 5.2.1.1 Suzuki-Miyaura cross coupling reactions of aryl halides and organoboronic acids The ligand system (t-Bu)2PFcC=NCH(CH3)R (Fc = ferrocenyl (C5H4)2Fe) is chosen as a model for this study because it contains both strong (phosphine) and weak (imine) donor sites and that they are separated by a conformationally flexible ferrocenyl skeleton which would in principle enable the weak donor to undergo facile reversible coordination.8a It is also important that both donating sites contain a substituent group that can be changed This allows the introduction of substituents (R or R’) to systematically and independently alter the electronic and steric properties of both sites.149 Within this ligand system, there are two types (Figure 5.3) The former (ligand L1a) has a fixed phenyl on the imine but the R on the phosphine varies, whereas the latter (ligand L1k-o) has a variable group on the imine with a constant tBu on the phosphine Ligand L1a is known to support Pd-catalyzed Suzuki coupling of aryl chlorides and aryl boronic acids8a-b and Ni-catalyzed ethylene oligomerization.8c R C=N-Ph C=N Fe Fe P(t-Bu)2 P(t-Bu)2 L1k, R = Ph L1l , R =p-tolyl L1m, R = p-f luorophenyl L1n, R = m-methoxyl L1o, R =Naphthyl L1a Figure 5.3 [P, N] ferrocenyl ligand synthesized in this study 99 Chapter We first compared the catalytic ability of L1a and L1k–o towards extremely hindered substrate combination involving 1-bromo-2-methylnaphthalene and 2-methylnaphthyl-1boronic acid in the presence of Pd2(dba)3 under typical Suzuki cross-coupling reactions (Table 5.1) Change of -Ph to -CH(CH3)(Ph) could be manifested in chelate dissociation and halide-bridge formation, thus reducing the metal sphere congestion promoting metalsubstrate interaction Indeed, a significant increase in the cross coupling product is observed (Table 5.1, entry and 2) It is evident that the product yields are sensitively dependent on R (Table 5.1, entry – 6) One possible explanation is the different oxidative addition products that are formed as a result of the hemilability of the ligands Table 5.1: Ligand effect on the Suzuki cross-coupling reactions of 1-bromo-2methylnaphthalene and 2-methylnaphthyl-1-boronic acid.a 1.2 mol% ligand 0.5mol% Pd 2(dba)3 + Br THF, Cs 2CO reflux, 24hr B(OH) Entry Ligand Isolated Yieldb L1a L1k 90 L1l 65 L1m 78 L1n 50 a 98 L1o equiv base Not optimized Isolated Yield is 100% if CsF is used b c Since L1o gives the highest yield in the above coupling, it is used as a model to examine the efficiency of sp2-sp2 Ar-Ar’ couplings (Table 5.2) The yields are satisfactory with many near-quantitative conversions Consistent with published results128a,e-f, sterically 100 Chapter demanding substrates require higher catalytic loads to achieve satisfactory yields (Table 5.2, entries 6-8).Cross-coupling using sterically bulky substrates to form tetra-orthosubstituted products were obtained in remarkably high isolated yields at low catalytic loads of 1.0 mol% Pd (Table 2, Entries 6-8) These catalyst loadings are comparable or lower than the reported catalyst systems.131-132 For example, only 0.1 mol% of Pd2(dba)3 (with 0.23 mol% of L1k) is sufficient to promote quantitative coupling of 1bromonaphthalene and naphthyl-1-boronic acid at r.t (Table 5.2, Entry 1) This is more favourable than the coupling of 1-bromonaphthalene and naphthyl-1-boronic acid at mol% of Pd(dba)2 and mol% of 134 at r.t over 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15.2100(11) c, Å 27.659(3) 18.6464(19) 17.6503(12) α, deg 90 94.371(3) 86.609(2) β, deg 90 94.356(3) 80.427(2) γ, deg 90 96.860(3) 83.410(2) 2523.6(4) 2261.9(4) 2907.4(4) cryst color V, Å 2 1.246 1.228 1.516 -1 abs coeff, mm 0.271 0.806 0.948 F(000) 1000 892 1356 θ range for data collection 1.47 to 25.00° 1.63 to 25.00° 1.75 to 27.50° index ranges no of reflns collected -10 ≤ h ≤ 11, 10 ≤ k ≤ 9, -32 ≤ l ≤ 6731 -11 ≤ h ≤ 11, -14 ≤ k ≤ 9, -22 ≤ l ≤ 22 13266 -14 ≤ h ≤ 14, -19 ≤ k ≤ 19, -22 ≤ l ≤ 22 38590 indep reflns 3723 (Rint = 0.0731) 7933 Rint = 0.0518 13339 Rint = 0.0537 max and transmission 0.9839 and 0.9328 0.9383 and 0.7940 0.8947 and 0.7641 no of 3723 / / 298 7933 / 121 / 532 13339 / 16 / 768 final R indices [I >2σ(I)] a, b R1 = 0.0840, wR2 = 0.1530 R1 = 0.0999, wR2 = 0.1957 R1 = 0.0652, wR2 = 0.1586 R indices (all data) R1 = 0.1115, wR2 = 0.1715 R1 = 0.1436, wR2 = 0.2125 R1 = 0.0978, wR2 = 0.1741 1.071 1.160 1.032 0.447 and -0.382 0.455 and -0.450 1.081 and -0.524 Z density, Mg/m data/restraints/params goodness-of-fit on F2 c large diff peak and hole, e Å a -3 R = (Σ|Fo| - |Fc|)Σ|Fo| b wR2 = [(Σ ω|Fo| - |Fc|)2/Σ ω|Fo|2]1/2 187 c GoF = [(Σ ω|Fo| - |Fc|)2/(Nobs-Nparam)]1/2 Table A2 Crystal Data and Structure Refinement Parameters for complexes C4, C5 and C7a complexes Empirical formula C4•C7H16Cl2 C65H54Cl3F10Fe2N2Ni2P2 C5 C32H37Cl3CrNOP2S C7a C30H32Cl3CrN2P2S Mr 1450.51 703.98 672.93 temp, K 223(2) 295(2) 223(3) Red Blue Blue cryst size, mm 0.34 x 0.20 x 0.18 0.10 x 0.08 x 0.06 0.10 x 0.08 x 0.02 cryst system Triclinic Monoclinic Monoclinic space group Pī P2(1)/c P2(1)/n a, Å 12.867(2) 13.308(3) 11.3331(13) b, Å 14.027(2) 14.316(3) 16.3009(19) c, Å 17.800(2) 17.351(4) 17.286(2) α, deg 100.472(3) 90 90 β, deg 106.307(3) 96.869(8) 99.248(4) γ, deg 90.936(4) 90 90 V, Å3 3024.2(8) 3281.7(12) 3151.8(6) cryst color 4 1.593 1.425 1.418 -1 abs coeff, mm 1.343 0.781 0.808 F(000) 1474 1460 1388 θ range for data collection 1.48 to 25.00° 1.54 to 25.00° 1.73 to 25.00° index ranges no of reflns collected -15 ≤ h ≤ 15, -16 ≤ k ≤ 16, -21 ≤ l ≤ 21 25829 -15 ≤ h ≤ 14, -17 ≤ k ≤ 15, -14 ≤ l ≤ 20 18581 -12 ≤ h ≤ 12, -17 ≤ k ≤ 19, -20 ≤ l ≤ 20 18076 indep reflns 9040(Rint = 0.1064) 5784(Rint = 0.2164) 5559(Rint = 0.1524) max and transmission 0.7940 and 0.6581 0.9546 and 0.9260 0.9840 and 0.9235 no of 9040/11/740 5783/118/407 5559/22/373 final R indices [I >2σ(I)] a, b R1 = 0.0695, wR2 = 0.1598 R1 = 0.1079, wR2 = 0.1590 R1 = 0.1175, wR2 = 0.1997 R indices (all data) R1 = 0.1330, wR2 = 0.1711 R1 = 0.2136, wR2 = 0.1913 R1 = 0.1920, wR2 = 0.2300 0.811 1.040 1.094 1.087 and -0.457 0.437 and -0.429 0.604 and -0.514 Z density, Mg/m data/restraints/params goodness-of-fit on F2 c large diff peak and hole, e Å-3 a R = (Σ|Fo| - |Fc|)Σ|Fo| b wR2 = [(Σ ω|Fo| - |Fc|)2/Σ ω|Fo|2]1/2 188 c GoF = [(Σ ω|Fo| - |Fc|)2/(Nobs-Nparam)]1/2 Table A3 Crystal Data and Structure Refinement Parameters for complexes C7b, C8 and C9 complexes Empirical formula C7b C31H34Cl3CrN2P2S C8 C32H34Cl3CrN2P2 2xC9•C2H3NO2 C54H53Cl6Cr2N3O6 P4 Mr 686.95 666.90 1280.57 temp, K 223(2) 223(2) 223(2) Blue Blue Purple cryst size, mm 0.18 x 0.06 x 0.02 0.20 x 0.08 x 0.06 0.10 x 0.08 x 0.06 cryst system Orthorhombic Orthorhombic Monoclinic space group Pbca Pbca P2(1)/c a, Å 11.213(2) 10.8132(9) 20.8878(15) b, Å 16.453(3) 17.3988(13) 18.7658(14) c, Å 34.755(7) 34.178(3) 15.4625(10) α, deg 90 90 90 β, deg 90 90 110.622(2) γ, deg 90 90 90 6414(2) 6430.1(9) 5672.6(7) cryst color V, Å 8 1.423 1.378 1.499 -1 abs coeff, mm 0.796 0.729 0.830 F(000) 2840 2760 2624 θ range for data collection 2.16 to 25.00° 2.23 to 25.00° 1.04 to 25.00° index ranges no of reflns collected -13 ≤ h ≤ 13, -19 ≤ k ≤ 15, -41 ≤ l ≤ 41 35350 -12 ≤ h ≤ 12, -20 ≤ k ≤ 19, -40 ≤ l ≤ 35 35585 -24 ≤ h ≤ 23, -22 ≤ k ≤ 21, -18 ≤ l ≤ 17 32273 indep reflns 5646(Rint = 0.1304) 5666 (Rint = 0.1468) 9999 (Rint = 0.1160) max and transmission 0.9843 and 0.8700 0.9575 and 0.8678 0.9519 and 0.9216 no of 5646/0/363 5666 / / 362 9999 / / 689 R1 = 0.0713, wR2 = 0.1314 R1 = 0.1024, wR2 = 0.1432 1.112 R1 = 0.0626, wR2 = 0.1120 R1 = 0.1026, wR2 = 0.1243 1.032 R1 = 0.1034, wR2 = 0.2122 R1 = 0.1626, wR2 = 0.2383 1.091 0.401 and -0.445 0.357 and -0.326 1.054 and -0.877 Z density, Mg/m data/restraints/params final R indices [I >2σ(I)] a, b R indices (all data) goodness-of-fit on F2 c large diff peak and hole, e Å a -3 R = (Σ|Fo| - |Fc|)Σ|Fo| b wR2 = [(Σ ω|Fo| - |Fc|)2/Σ ω|Fo|2]1/2 189 c GoF = [(Σ ω|Fo| - |Fc|)2/(Nobs-Nparam)]1/2 Table A4 Crystal Data and Structure Refinement Parameters for complexes L5, (R)C16a and (S)-C16a complexes Empirical formula Mr L5 C26H25NO2P2 (R)-C16a•C6H11.50Cl1.50O1.50 C49H53.50BCl1.50F4FeNO1.50PRh (S)-C16a•C6H12Cl1.50O1.50 C49H54BCl1.50F4FeNO1.50PRh 445.41 1010.14 1010.65 temp, K 223 (2) 223(2) 223(2) Colourless Orange Red cryst size, mm 0.26 x 0.20 x 0.14 0.86 x 0.22 x 0.08 0.86 x 0.22 x 0.08 cryst system Monoclinic Triclinic Triclinic space group C2/c P1 P1 a, Å 20.424(15) 10.1370(5) 10.1234(6) b, Å 8.974(7) 11.0821(6) 11.0655(7) c, Å 12.342(9) 20.1903(11) 20.1676(12) α, deg 90 87.6030(10) 87.3770(10) β, deg 99.544(15) 84.6930(10) 84.4320(10) γ, deg 90 87.6290(10) 87.4130(10) 2231(3) 2254.9(2) 2244.3(2) cryst color V, Å 2 1.326 1.488 1.496 -1 abs coeff, mm 0.219 0.868 0.872 F(000) 936 1038 1039 θ range for data 2.02 to 27.50° 1.84 to 27.50 1.84 to 27.50 -26 ≤ h ≤ 26, -5 ≤ k ≤ 11, -16 ≤ l ≤ 15 7201 -13 ≤ h ≤ 13, -14≤ k ≤ 14 -26 ≤ l ≤ 26 29499 -13 ≤ h ≤ 13, -14≤ k ≤ 14 -26 ≤ l ≤ 26 28441 2551 (Rint = 0.0751) 0.9700 and 0.9453 20499 (Rint = 0.0296) 20313 (Rint = 0.0341) 0.9338 and 0.5223 0.9335 and 0.5209 2551 / 21 / 151 20499/139/1093 20313/137/1060 R1 = 0.0827, wR2 = 0.2262 R1 = 0.0492, wR2 = 0.1167 R1 = 0.0679, wR2 = 0.1378 Z density, Mg/m collection index ranges no of reflns collected indep reflns max and transmission no of data/restraints/ params final R indices [I >2σ(I)] a, b R1 = 0.1079, R1 = 0.0529, R indices (all data) wR2 = 0.2453 wR2 = 0.1196 goodness-of-fit 1.068 1.017 on F2 c large diff peak 0.871 and -0.459 0.856 and -0.499 and hole, e Å-3 a R = (Σ|Fo| - |Fc|)Σ|Fo| b wR2 = [(Σ ω|Fo| - |Fc|)2/Σ ω|Fo|2]1/2 190 R1 = 0.0631, wR2 = 0.1414 1.051 1.199 and -0.928 c GoF = [(Σ ω|Fo| - |Fc|)2/(Nobs-Nparam)]1/2 ... enantioselective reduction of ketones to secondary alcohols They are nitrogenbased chelating ligands, diphosphines and heterobidentate [P, N] ligands 6.1.3.1 Nitrogen-based ligands A number of highly efficient... The mixture of Pd2(dba)3, ligand and chloroform were made Preliminary analyses were performed on a one-pot reaction of Pd2(dba)3, ligand L1k in chloroform stirred at temperature of 60°C for h... result of the hemilability of the ligands Table 5.1: Ligand effect on the Suzuki cross-coupling reactions of 1-bromo-2methylnaphthalene and 2-methylnaphthyl-1-boronic acid.a 1.2 mol% ligand 0.5mol%