Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141

Rhodium-catalyzed hydroformylation of allylbenzenes and propenylbenzenes: effect of phosphine and diphosphine ligands on chemo- and regioselectivity
Ana C. da Silva, Kelley C.B. de Oliveira, Elena V. Gusevskaya1 , Eduardo N. dos Santos∗
Departamento de Qu´ ımica-ICEx, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte MG, Brazil Received 11 June 2001; accepted 9 October 2001

Abstract Various allylbenzenes and propenylbenzenes have been hydroformylated with a 97–99% chemoselectivity using bis[(␮-acetate)(1,5-cyclooctadiene)rhodium(I)] as a catalyst precursor. Regioselectivity of the hydroformylation can be controlled by the nature of phosphorus auxiliary ligands. The Rh-NAPHOS (2,2 -bis[(diphenylphosphino)methyl]-1,1 -binaphthyl) system promotes the hydroformylation of allylbenzenes into linear aldehydes in near 95% selectivity and propenylbenzenes into branched aldehydes with a formyl group in ␣-position to phenyl ring in near 90% selectivity, while the Rh-dppp (1,3-bis(diphenylphosphino)propane) system gives branched aldehydes with a formyl group in ␤-position in near 70% selectivity starting from allylbenzenes. The regioselectivity of Rh-diphosphine systems correlates with a ligand bite angle. Both the rate and regioselectivity of the hydroformylation are largely influenced by the basicity of monophosphine auxiliary ligands, however, no correlation between their steric characteristics and the regioselectivity has been observed. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Allylbenzenes; Regioselectivity; Hydroformylation; Ligands

1. Introduction Selective functionalization of naturally occurring special olefins can provide oxygenated derivatives which are valuable materials in the fine chemicals industry. We have recently reported that allylic acetates, alcohols, aldehydes and carboxylic acid derivatives can be obtained in good yields by the metal complex catalyzed oxidation [1,2], hydroformylation [3,4] and alkoxycarbonylation [5] of some monoterpenes.
∗ Corresponding author. E-mail addresses: elena@dedalus.lcc.ufmg.br (E.V. Gusevskaya), nicolau@dedalus.lcc.ufmg.br (E.N. dos Santos). 1 Co-corresponding author.

Hydroformylation represents a versatile method for the production of commercially important aldehydes and alcohols, which are difficult to obtained by the conventional synthetic pathways. Aldehydes derived from substituted allylbenzenes and propenylbenzenes (Scheme 1), easily available from biomass, show biological and phytosanitary activities and are also useful in flavor, perfume and pharmaceutical industries [6,7]. However, the hydroformylation of these olefins has only little been studied hitherto [7–10]. High-pressure (600 MPa) hydroformylation of eugenol (1a) and isoeugenol (2a) results in a mixture of aldehydes 3a, 4a and 5a, with regioselectivity being depending on temperature [7]. Aldehyde 3a was obtained up to 95% selectivity from 2a, while 1a gave in all

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88 and 80% selectivities for linear aldehydes 5a–5d. 4a and 5a) aldehydes.5cyclooctadiene)rhodium(I)] as a catalyst precursor.and rhodium-catalyzed hydroformylation of estragole (1d) and its isomer anethole (2d) has been reported recently [10]. 2. The aim of this work was to study the effect of various phosphine and diphosphine ligands on the hydroformylation of allylbenzenes 1a–1c and propenylbenzenes 2a and 2c using bis[(␮-acetate)(1.1 -biphenyl (BISBI) were kindly donated by Prof.9] studied the hydroformylation of 1a–1d using [Rh2 (␮-SR)2 (CO)2 L2 ] as a catalyst precursor and achieved 96. B.2 -Bis[(diphenylphosphino)methyl]-1. with low regioseletivity for aldehydes 4d and 5d. Mass spectra were . Hanson (Virginiatech. Bis[(␮-acetate)(1. We found that chemo. US). Enantioselective platinum/tin. The products were analyzed by gas chromatography (GC) using a Shimadzu 14B instrument fitted with a Carbowax 20 M capillary column and a flame ionization detector.2 -bis[(diphenylphosphino)methyl]-1. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 Scheme 1.and regioselectivity can be controlled by the ligand nature and developed the systems offering the preferential synthesis of either branched 3a and 3c (in near 90% regioselectivity). branched 4a–4c (in near 70% regioselectivity) or linear 5a–5c (in near 95% regioselectivity) aldehydes in very high chemoselectivities (>97%).5-cyclooctadiene)rhodium(I)]—[Rh (COD)(OAc)]2 —was prepared by published procedure [11]. unless otherwise indicated. Experimental All chemicals were purchased from Aldrich and used as received. Kalck et al.134 A. Benzene was purified under reflux with sodium wire/benzophenone for 6 h and then distilled under nitrogen. da Silva et al. however. cases the comparable amounts of two (4a and 5a) or three (3a. NMR spectra were obtained using a Brucker CXP-400 spectrometer with tetramethylsilane as an internal standard in CDCl3 . respectively. 2. [8.C.1 binaphthyl (NAPHOS) and 2. The branched aldehydes derived from allylbenzenes and propenyl- benzenes are precursors of various pharmacologically important compounds [10]. 86.

1H. 3 J = 7. 3 J = 6. 2. CH2 ).72 (Ar). int.32 (CH ).4-Dimethoxybenzyl)-propanal (4b). and 13 C-NMR spectroscopy.67 (s. 11. int. 3. 3.4 Hz. placed in an oil bath.71 (d. 1 H-NMR: δ . 3H. 133.60 (CHO). 1H.A. 143.64 (d. COSY and DEPT NMR experiments. 122. 1 H-NMR: δ . Ar: CHCHCOH).66–1. 135/195 (M+ −C2 H4 CHO).55 (dd.1 Hz. 3.): 194/17 (M+ ).4 Hz. 9. The assignment of 1 H and 13 C-NMR signals was made using HMQC.49 (Ar: CHCOH).12 (m. 13. 1 H-NMR: δ .6 Hz. 13 C-NMR: δ . 1H. 3 J = 8.17 (O–CH2 –O).6 Hz. OCH3 ). Spectral simulations performed with the ADC/ CNMR program were in agreement with the spectra observed.2 Hz. 204. 3 J = 2.84 (s.1 Hz. 3.84 (CH2 ). 3 J = 8.57 (t.50 (Ar: COCH3 ).64 (m.64 (Ar: CCHCHO). 3 J = 7. 11.5 Hz.5 Hz.21 (Ar).81 (s. 3 J = 8.59–6.70 (Ar).80 (m. OCH3 ). 1. 3H.99 (Ar: COCH3 ). OCH ). int. CH2 ). 0. 200. 6. After carrying out the reaction and cooling to room temperature. 60. 23. 133. 3H. 2 6.06 (Ar: CHCOCH3 ). 151/100 (M+ −C2 H4 CHO).70 (Ar). 3 J = 1. 3 J = 8. 9. OCH3 ). CH2 ). 1H. 3 J = 8. 120. 111. 1H.62–1.0 Hz. 147. 130. 3H. CH2 ).27 (Ar: COCH2 ). 6. 3 J = 1. 3 J = 7. CHCHO).73 (Ar).20 (CH2 CH2 CHO).60 (CH2 ). 2. O–CH –O).60 (m. CHO). 55.27 3 2 (CHCHO). 2H.67 (CH3 ). 13 C-NMR: δ .62 (Ar). 3. 2. 1.8 Hz. Ar: CHCOCH3 ). CHO). 12. MS (m/z/rel.6 Hz.40 (CH2 CHO). 1. 130. 1H.63 (d. MS (m/z/rel. 2H.76 (Ar: CHCHCOH). 35. CHO).4 Hz.77 (Ar: COCH3 ).70 (Ar). 3.42 (CHCHO). CHCHO). 137/100 (M+ −C2 H4 CHO). 1. 203. 42. 9. 1. 1H. 3. MS (m/z/rel.4 Hz.95–2. 9. 6. 3H. 0. 1 H.6 Hz.32 (td. CH2 CH2 CH2 ).84 (d. 137/100 (M+ −C2 H4 CHO). 2. 13 C-NMR: δ . 22. substrate (10. 121. 3H. 146. 6. 3 J = 5.69 (Ar: CCH2 ). 55.20 (OCH3 ).83 (CHO).63 (CH3 ). 108. 114. 111. 1H.20 (Ar). 147. 3 J = 7. 23. 1H.98 (dd.32 (Ar: COCH3 ). / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 135 obtained on a Hewlett-Packard MSD 5890/Series II instrument operating at 70 eV.2 Hz. 146. 3 J = 7.86 (Ar). 2. 2. 108. OCH3 ).2 Hz.10–0.99 (OCH3 ). 2H. 201. 2-(4-Hydroxy-3-methoxyphenyl)-butanal (3a). 3H. 3. 2 CH2 CH2 CH2 ).93 (CH2 ). 111. 121.48 (CHO). CHCHO). 145. Ar: CHCHCOH).59 (Ar: COH).80 (m. 148. 36. 6. CH2 ).3 Hz.0 Hz. 3 J = 1.): 194/17 (M+ ). 146.75 (m. 1. 5. a mixture of [Rh(COD)(OAc)]2 (0. 1 H-NMR: δ .0 mmol).82 (d. and benzene (40 ml) was transferred from a Schlenck tube under nitrogen into a stainless steel magnetic stirred autoclave. 1 H-NMR: δ .65 (d.40 (td.40 (CHCHO). 1H.32 (Ar: CCH2 ). 6. 163/100 (M+ −CHO). 120.12 (OCH3 ). Ar). 145. 110.4-Dimethoxyphenyl)-butanal (5b). 2-(4-Hydroxy-3-methoxybenzyl)-propanal (4a).0 Hz.90 (qi.91 (qi. 3H. 2.75 (CHO).32 (Ar: COCH3 ). OCH3 ). 3 J = 7.57 (t.12 (OCH3 ). 2-(3. 6. 3 J = 7. Ar). 2-(3. Ar: CHCOH). 2H.70 (CHO). 2.87 (Ar: CHCHCOH).1 Hz. 3. CH3 ).01 (dd. 2H. CHCHO). 2 J = 12. 60. 1H.87 (s. 148. 127.69 (t. 146. 3 J = 7. 13 C-NMR: δ .95 (Ar: CHCOCH3 ). 3H. 101. 9. 2H.05 (d.): 192/15 (M+ ). 42. CH3 ).80 (Ar: CCH2 ). da Silva et al. 1H.81 (Ar). CH2 CH2 CHO).20 mmol).): 194/24 (M+ ). and stirred.01 (Ar: COH). 119. phosphine or diphosphine (0. 3H.66–6.2 Hz. 3 J = 7.5 Hz. CH2 ). In a typical run.91 (d. 1H. 13 C-NMR: δ . 132. 1H. 1H.94 (OCH3 ). 6.81 (m.41 (Ar: COH). 55.5 Hz. 3H.4 Hz. 1. 1H.77 (CH2 CH2 CHO). 48.44 (td. 1H. 2. 148.C. int.06 (Ar: COCH2 ). 3 J = 8. 2 J = 13.0 Hz. the excess CO and H2 were slowly vented.): 164/66 (M+ −CH3 CHO).96 (s. 110.65–6. CHO). 1H.54 (CH2 CH2 CH2 ). CH3 ). 3 J = 1. OCH3 ).5 Hz.): 151/100 (M+ −C2 H4 CHO). Ar: CHCOH). 202. 114.71 (dd.45 (CHCHO). 3 J = 2. CHO).0 Hz. 9. 3 J = 6.95 (CH2 CHO). 1H.0 Hz. 34.61–2. 2H.02–2.84 (s. 111. 1H. Ar: CHCOH).79 (Ar: COCH3 ). 4-(4-Hydroxy-3-methoxyphenyl)-butanal (5a).4-Methylenedioxyphenyl)-butanal (3c).21 (Ar: CHCOH).85 (s. and identified by GC/MS.33 (td.60–2.65 (d.51 (CHO). 2. 150/90 (M+ −CH3 CHO). 2H. 200. 55. The products were separated by column chromatography (silica) using mixtures of hexane and CH2 Cl2 as eluents. CH2 CHO).6 Hz.87 (s. 3. 55.5 Hz. CH2 ). The solution was analyzed by GC and GC/MS. aromatic (Ar): CHCOCH3 ). int.005 mmol).01 (Ar: CCH2 ). 42. 1H. CH2 ).73 (t. 4 J = 2.1 Hz.5 Hz. 3 J = 1.75 (OCH3 ). 2 J = 13.20 (OCH3 ). CH CHO).53 (CH ).90 (t. MS (m/z/rel.9 Hz.81 (s. CHO). CH3 ). 22. 6. . 3 J = 7. 110.52 (Ar: CHCH2 ).53–2. 55. 1H. 137/100 (M+ −C2 H4 CHO). 3 1H. 1 H-NMR: δ . 3 J = 2. 3H.0 Hz. The reactor was pressurized to 2 MPa total pressure (CO/H2 = 1/1). int. 165/197 (M+ −CHO). 34.20 (Ar: COCH3 ). 4-(3. 114. Reactions were followed by a gas–liquid chromatography using a sampling system. 1H. 3 J = 6. 3 J = 7.63 (d.50 (CH3 ).66–6.66 (m. 3 J = 2.09 (d. 3H. CH2 CH2 CHO). 6. 4 J = 2.83 (m. MS (m/z/rel. 1H.90 (t. 13 C-NMR: δ .68 (m.86 (Ar: CHCOH).0 Hz. 55. Ar). Ar).41 (Ar). MS (m/z/rel. 3 J = 1.13 (m. 3H.00 (CH2 CH2 CH2 ).

respectively). 3H. 51/32. 5. 2. Only trace amounts of the hydrogenated substrate are formed. in the presence of triphenylphosphine. CHO). 145. 3. MS (m/z/rel. O–CH2 –O).99 (dd. 1H. 2H.005 mmol). c Selectivity for the hydroformylation products.2 Hz.e 42 4a 20 28 18 5a 48 72 40 a Reaction conditions: substrate (10. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 2-(3.0 mmol).C. 147.136 A. respectively.42 (Ar: CHCH2 ). Moreover. 1H. 3H. 147. b Reaction time necessary for a 100% conversion. 3 J = 5. 2 MPa) with [Rh(COD)(OAc)]2 used as a catalyst precursor. 4-(3 -Methylenedioxyphenyl)-butanal (5c). Thus. 2. 1.83 (O–CH2 –O).14 (CHCHO).83 (O–CH2 –O). 60 ◦ C. These results are completely consistent with the expected mechanism of eugenol hydroformylation and isomerization. Chemoselectivity is determined by relative reactivity of the branched alkyl intermediate towards carbonylation vs.10 mmol). 1. d Determined by GC. benzene (40 ml). 121. 108. 2. 109. Ar).2 Hz. the ␣-isomer has not been detected under the conditions used because of the lower reactivity of internal olefins in hydroformylation. 6. 3 J = 1. with hydrogen being abstracted from the ␣-carbon. 2. 148/100 (M+ −CH3 CHO). 34.5 Hz. 145.55 (m. However.5 Hz.92 (s. 135/100 (M+ −C2 H4 CHO). Table 1 Hydroformylation of eugenol (1a) catalyzed by [Rh(COD)(OAc)]2 : effect of phosphorus ligand additiona Run Ligand Timeb (h) Selectivityc . 100. int. int.76 (Ar).): 192/25 (M+ ).): 192/20 (M+ ). 36.51–2.23 (Ar). 2H. 1H. run 3). 1 H-NMR: δ . it was found [12] that the more nucleophilic the incoming ligand at the migration of the alkyl group to a cis-CO.5 Hz. O–CH2 –O). OPPh3 (Table 1.75 (t.93 (CH2 CHO).08 (d. run 1) occurs smoothly under mild conditions (60 ◦ C. In an attempt to clarify the effect of phosphorus ligand nature and control the regioselectivity driving the reaction towards either the linear or branched aldehydes. When triphenylphosphine is substituted by a less basic ligand.09 (CH3 ).17 (Ar).58–6. 2 J = 12. 108.and ␤-carbons. 100. CH2 CH2 CH2 ).63 (m. 2H. CH2 CH).58–6. 2 MPa (CO/H2 = 1/1).92 (s. [Rh(COD)(OAc)]2 (0.8 Hz. 2H. in the absence of auxiliary phosphorus ligand. should disfavor the hydride transfer from the ␣-carbon to the rhodium atom bearing now a less positive partial charge. 1 H-NMR: δ . CHO). It is expected to be strongly affected by the ligand basicity. near 30% of isoeugenol 2a is formed along with branched (4a) and linear (5a) aldehydes (5a/4a = 2. 9. the faster the carbonylation step. CH2 CHO). CH3 ). 2H. 3H. 13 C-NMR: δ . run 2). 204. 3 J = 7. da Silva et al.59 (Ar: COCH2 ).95 (Ar: CCH2 ). giving rise to a full conversion of the substrate within 3 h.35 (CHO).75 (m. 108.57 (t.45 (CHO). hydrogenated substrate is detected in trace amounts.5 Hz.1) (Table 1. the product distribution is rather similar to that observed in the absence of any auxiliary ligand (run 1). CH2 CH2 CHO).5 Hz. 13.17 (Ar). 1H. 77/44. 121.91 (qi. 9. we have studied the hydroformylation of eugenol 1a in the presence of various phosphine (Table 2) and . Ar). 5. The addition of triphenylphosphine (P/Rh = 10) dramatically improves the chemoselectivity of hydroformylation (up to nearly 100%) with the linearity being almost the same (5a/4a = 2.31 (CH2 CH). which is more basic ligand than CO. As a result. 3 J = 7. MS (m/z/rel.5 Hz.86 (Ar). 3 J = 7. 134. however. 2. 3 J = 1. 202. d (%) Product distributiond (%) 2a 1 2 3 None PPh3 OPPh3 3 5 3 69 100 58 31 tr. 3 J = 6.74 (Ar: COCH2 ). 42.5 Hz. 13 C-NMR: δ .75 (m. Results and discussion Hydroformylation of eugenol 1a (Table 1.11 (Ar).69 (d. 23. 3 J = 7. The former then originates a linear aldehyde. Hydroformylation of 2a would give branched aldehydes 3a and 4a with the formyl group in ␣. The addition of rhodium(I) hydride to the coordinated olefin results in linear and branched rhodium alkyl intermediates (rhodium attached to ␥. 135/100 (M+ −C2 H4 CHO). CH2 CH).64 (CH2 CH2 CH2 ).79 (CH2 CH2 CHO).and ␤-positions. 6. ␤-hydride elimination.44 (td.59–2. e Trace amounts. 3 J = 1. phosphorus ligand (0. 77/19. 1H. The presence of PPh3 .4). the carbonylation of the alkyl intermediate is strongly favored. while the latter could give either branched aldehyde 4a via carbonylation or isomeric olefin 2a via a rhodium hydride elimination. CHCHO). hydroformylation is strongly complicated by the excessive isomerization of a terminal C=C double bond. 132.4-Methylenedioxybenzyl)-propanal (4c). 48.59 (Ar: COCH2 ).74 (Ar: COCH2 ).

[Rh(COD)(OAc)] (0. The ligand cone angles. [Rh(COD)(OAc)] (0. benzene (40 ml).3-bis(diphenylphosphino)propane. [13]. The obtained results are in full agreement with the usually observed effects of ligand Table 3 Hydroformylation of eugenol (1a) catalyzed by [Rh(COD)(OAc)]2 /diphosphine systemsa Run Diphosphineb Bite anglec (◦ ) Time (h) Conversiond (%) Product distributiond (%) 4a 1 2 3 4e 5e dppe dppp dppb BISBI NAPHOS 85 91 98 123 120 24 24 24 7 7 55 74 99 81 90 62 69 34 2 2 5a 38 31 66 98 98 5a/4a 0. In all the cases. respectively.0 mmol).9 49. phosphorus ligand (0. as proposed by Tolman [13].10 mmol.C. The higher the cone angle. c From Ref. tribenzylphosphine. . θ . NAPHOS: 2.2-bis(diphenylphosphino)ethane. 80 ◦ C. dppp: 1. tri(n-butyl)phosphine. P(CH2 Ph)3 . da Silva et al.0 a Reaction conditions: substrate (10. P(Cy)3 . We chose a series of phosphines exerting different steric and electronic effects: triphenylphosphine.9 2066. Two groups of ligands with significantly different basicity are presented in Table 2: PPh3 /P(CH2 Ph)3 and P(n-Bu)3 /P(Cy)3 .16].0 mmol).1 2056. P(n-Bu)3 .1 -binaphthyl. the greater steric crowding the phosphine ligand introduces to the metal center. which transfers some of this increase along to the coordinated carbon monoxide by back donation.2 a Reaction conditions: substrate (10. no appreciable double bond isomerization was observed. 2 MPa 2 (CO/H2 = 1/1).1 1. f Determined by GC. b Bu: butyl.1 -biphenyl.5 1. while the systems with P(n-Bu)3 and P(Cy)3 require 5–7 h to reach a 100% conversion (runs 3 and 4). diphosphine (Table 3) ligands.1 1.2 -bis[(diphenylphosphino)methyl]-1. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 137 Table 2 Hydroformylation of eugenol (1a) catalyzed by [Rh(COD)(OAc)]2 /L systems: steric and electronic effects of auxiliary phosphorus ligand (L)a Run Ligandb Cone anglec (◦ ) ν c . Thus.10 mmol).6 0.1 2.4-bis(diphenylphosphino)butane.A.20 mmol). The stronger donor phosphines increase the electron density on Ni. d ν (CO) of Ni(CO) L in CH Cl . [15. The systems with weaker donor phosphines (runs 1 and 2) show much higher activity in hydroformylation of eugenol converting 100% of the substrate for 1–2 h. d Determined by GC. the ν (CO) frequency becomes lower with increase in the phosphine basicity. 80 ◦ C. hydrogenated substrate is detected in trace amounts. and ν (CO) frequencies of a series of complexes of the type Ni(CO)3 L were taken as the quantitative measures of steric and electronic effects. e Diphosphine: 0. d (cm−1 ) Timee (h) Product distributionf (%) 4a 1 2 3 4 PPh3 P(CH2 Ph)3 P(n-Bu)3 P(Cy)3 145 165 132 170 2068. 2 MPa 2 (CO/H2 = 1/1). dppb: 1. BISBI: 2. b dppe: 1.005 mmol). tricyclohexylphosphine. diphosphine (0. PPh3 .005 mmol). with the phosphines of the latter group being more basic than those of the former.0 49.2 -bis[(diphenylphosphino)methyl]-1. 3 2 2 e Reaction time necessary for a 100% conversion.4 1 2 7 5 31 32 48 45 5a 68 68 52 55 5a/4a 2. Cy: cyclohexyl. c From Ref. benzene (40 ml). hydrogenated substrate is detected in trace amounts.4 2056.

the system with 1. dppp which raises the chance of an arm-off ␩1 -coordination [15]. patented by Eastman Kodak in 1987 [18]. which transfers some of this increase along to the coordinated hydride facilitating its nucleophilic interaction with ␥-carbon. both the preference of these chelates to occupy diequatorial sites in the trigonal-bipyramidal intermediate and their increased steric bulk more likely contribute to this effect [15.3-bis(diphenylphosphino)propane (dppp).138 A. .17].4-bis(diphenylphosphino)butane (dppb). Excellent linearities of up to 98% are achieved with BISBI and NAPHOS (runs 4 and 5). as discussed above.17]. The branched aldehyde is formed via a hydride ligand transfer to the ␥-olefinic carbon which bears a more positive fractional charge compared to the ␤-carbon (Scheme 1). we believe that active species containing one phosphine ligand seem to operate in the regioselectivity determining step under the conditions used. they “block” the active center. the apical hydride is trans to the phosphine ligand and is expected to be less acidic than the hydride of the BISBI and NAPHOS complexes. ca. On the other hand. while the use of 1. Thus. it can be seen from the data in Table 2 that the stronger donor phosphines P(n-Bu)3 and P(Cy)3 favor the formation of branched aldehyde 4a in larger amounts (5a/4a is ca.2-bis(diphenylphosphino)ethane (dppe) and 1.e. more bulky phosphines would strongly favor the formation of a less sterically crowded straight chain ␴-alkyl rhodium intermediate enhancing a terminal hydroformylation. Ligand natural bite angles near 90◦ would induce an apical-equatorial coordination of bidentate dppe and dppp ligands in a trigonal-bipyramidal rhodiumolefin-hydride intermediate. da Silva et al. With BISBI and NAPHOS. the less active they are [14]. with the substituent at the olefinic bond oriented to the opposite to hydride ligand side of the equatorial plane) becomes. bite angles near 90◦ [15]. This is highly unexpected if intermediate complexes with more than one phosphine ligand. bisligand and trisligand species. in the five-coordinated Rh-dppe and Rh-dppp intermediates. which is almost the same as that of monodentate triphenylphosphine (cf. and 132◦ for P(n-Bu)3 vs. This increase in the electron density on hydride facilitates its nucleophilic interaction with ␥-carbon of the coordinated olefin resulting in branched aldehyde 4a. are involved in the step which determines the reaction regioselectivity. Hydroformylation of eugenol 1a in the presence of various diphosphine auxiliaries. is presented in Table 3. The more basic phosphines increase the electron density on Rh. Although the reasons for the increased regioselectivity of hydroformylation seen for diphosphines with large natural bite angles are not yet fully understood. Phosphines with the similar basicity but with very different cone angles (145◦ for PPh3 vs. which usually give an enhanced preference for bis(phosphine)rhodium complexes and offer more control over regiose- lectivity [15]. Thus. Indeed.. i. promotes the fastest hydroformylation (run 1). switches the selectivity from linear to branched aldehyde (up to ca. bite angles near 120◦ [15. which is trans to a less basic CO ligand. Due to their strong coordination to the metal. 170◦ for P(Cy)3 ) showed rather similar results in eugenol hydroformylation. the more nucleophilic the hydride is in a trigonal-bipyramidal intermediate. An analysis of the data presented in Table 2 reveals that there is no correlation between the steric characteristics of the phosphines studied and regioselectivity of the catalytic system. while BISBI and NAPHOS with bite angles near 120◦ enforce a diequatorial chelation [15. the more preferable the equatorial coordination of eugenol to Rh in the way which favors the hydride addition to the terminal ␥-carbon (i. In addition. 70% of ␤-isomer 4a) (runs 1 and 2). which is expected to bind as an apical-equatorial chelate. Different efficiency of dppb compared to dppp was earlier observed in various reactions. In this case.C. It could be explained by increasing flexibility of a ligand backbone in dppb vs. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 basicity on the hydroformylation rate: the more basic the phosphines. both the rate and regioselectivity of eugenol hydroformylation are largely influenced by basicity of phosphine auxiliary ligands. and run 1 in Table 2). we have found that the reaction regioselectivity depends on the diphosphine nature and clearly correlates with ligand bite angles.e. bite angle 98◦ . 1 in runs 3 and 4 vs. as the poorest ligand in this series. 165◦ for P(CH2 Ph)3 . PPh3 . 2 in runs 1 and 2). run 3 in Table 3. High selectivity towards linear aldehydes of a BISBI-based rhodium catalytic system.. As far as regioselectivity is concerned. the linearity is as high as 98% (runs 4 and 5).16]. Thus. was also observed in the hydroformylation of 1-hexene [19] and 1-octene [20]. does not promote the preferential formation of branched aldehydes and show a 66% linearity.

in addition.10 mmol). benzene (40 ml). with a positive partial charge being expected on ␣-carbon atoms due to the M+ effect of the phenyl ring.2 -bis[(diphenylphosphino)methyl]-1. 1 2 1a 1b 1c 1a 1b 1c dppp dppp dppp NAPHOS NAPHOS NAPHOS 74 50 62 100 100 100 tr.C. NAPHOS (0. conjugated with the phenyl ring. c Determined by GC. reaction time = 24 h.d tr. The double bonds in these substrates are internal and.3-bis(diphenylphosphino)propane. d Trace amounts. Hydroformylation of 2a and 2c expectedly proceeds at much slower rates.2 -bis[(diphenylphosphino)methyl]-1. Only 14% conversion of 2a occurs for 24 h under the conditions similar to those used for allylbenzenes (run 1). tr.1 -binaphthyl. i. da Silva et al. eugenol methyl ether 1b and safrol 1c. Aldehyde Table 5 Hydroformylation of propenylbenzenes 2a and 2c catalyzed by [Rh(COD)(OAc)]2 a Run Substrate Auxiliary ligandb Pressure (MPa) Temperature (◦ C) Time (h) Conversionc (%) Product distributionc (%) 3 76 41 45 32 28 63 92 74 93 4 24 56 52 53 44 26 5 21 4 5 – – – 12 19 – – – 2 Hydrogenated substrate – 3 3 3 9 11 3 5 1 1 2 3d 4d 5 6 7 8 9 2a 2a 2a 2a 2a 2a 2a 2c 2c None None None None None dppp NAPHOS dppp NAPHOS 2 6 6 6 9 9 9 9 9 80 80 80 100 130 130 130 130 130 24 6 6 6 4 24 24 24 24 14 82 73 80 100 53 52 54 54 a Reaction conditions: substrate (10. b dppp: 1. 2 .1 -binaphthyl.. b dppp: 1. i. than that of allylbenzenes. 1 2 tr. c Determined by GC.3-bis(diphenylphosphino)propane.A.20 mmol). Excellent chemoselectivity is achieved in all cases with only small amounts (2%) of the hydrogenated substrate being detected. NAPHOS: 2. auxiliary ligand (if any) (0. 2 CO/H2 = 1/1. 3 1 Reaction conditions: substrate (10.005 mmol). Starting from naturally occurring isomers of eugenol and safrol. while the Rh-dppp catalyst allows the preferential formation of the branched aldehydes (␤-isomers) (runs 1–3). [Rh(COD)(OAc)] (0. NAPHOS: 2. The Rh-NAPHOS catalyst converts 1a–1c into corresponding linear aldehydes 5a–5c in a 90–98% regioselectivity (runs 4–6).0 mmol).e. dppp (0. 80 ◦ C.20 mmol).005 mmol). The rhodium-diphosphine systems were found to be also very efficient in controlling the regioselectivity of the hydroformylation of other allylbenzenes. propenylbenzenes 2a and 2c. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 Table 4 Hydroformylation of allylbenzenes 1a–1c catalyzed by [Rh(COD)(OAc)]2 /diphosphine systemsa Run Allylbenzene Diphosphineb Conversionc (%) Product distributionc (%) 2a–2c 1 2 3 4 5 6 a 139 4a–4c 69 66 65 2 6 5 5a–5c 31 33 33 98 90 93 Hydrogenated substrate tr. The results are presented in Table 4.0 mmol).e. [Rh(COD)(OAc)]2 (0. it is possible to obtain selectively the other branched aldehydes—␣-isomers 3a and 3c (Table 5). benzene (40 ml). tr. 2 MPa (CO/H2 = 1/1). d CO/H = 2/1.

while in the systems with dppp. run 5). All these reactions proceed with very high chemoselectivities (97–99%). NAPHOS promotes the formation of more sterically hindered ␣-aldehydes 3a and 3c in higher than 90% selectivity. 4a and 5a in comparable amounts is formed along with 9% of hydrogenated substrate. it fails to explain the higher regioselectivity of the Rh-NAPHOS catalyst (Table 5. the larger amounts of the branched aldehyde with the formyl group in a sterically more demanding ␣-position are formed. pressure and CO/H2 ratio (runs 1–5). the partial isomerization of 2a into 1a and fast hydroformylation of the latter occurs in the reaction solutions. da Silva et al. Interestingly. e. 4. The regioselectivity of the Rh-diphospine .g. run 5). The reasons for the correlation between the ligand bite angle and regioselectivity in hydroformylation have been widely discussed. while the hydride of the Rh-NAPHOS complexes is trans to a less basic CO ligand and would be expected to be more acidic. Conclusions This study shows that chemo. bite angle 91◦ . the selectivity for 3 is much lower (63–76%. in which the apical hydride of the intermediate in the regioselectivity determining step is also trans to a CO ligand.140 A. not only the nature of the ligand trans to the apical hydride. run 7) compared to the unprompted rhodium system (Table 5. The introduction of auxiliary diphosphines. because despite the increase of the effective steric bulk compared to dppp. hydroformylation has been accelerated significantly (100% conversion for 4 h. dppp or NAPHOS. Undoubtedly. at the expense of regioselectivity—a mixture of all three isomeric aldehydes 3a. Such a consideration gives a reasonable explanation for the increase in selectivity for ␣-aldehydes in going from the Rh-dppp to Rh-NAPHOS catalyst. In the five coordinated Rh-dppp complex. lowers the hydroformylation rate and strongly orients the selectivity towards ␣-isomer 3a (runs 6–9 vs. have showed much higher linearity in hydroformylation of terminal olefins than diphosphines with bite angles near 90◦ and enhanced preference to form apical-equatorial complexes. This results in the formation of branched aldehydes 3a and 3b with the formyl group incorporated in ␣-position. the natural bite angle of the chelating diphosphine dramatically influences the regioselectivity. the apical hydride is trans to the strong donor phosphine. As-mentioned above. Decreasing the electron density on hydride facilitates its interaction with a ␤-carbon atom of the coordinated olefin bearing a negative partial charge. NAPHOS with bite angle of 120◦ gives 92–93% of ␣-isomer 3 (runs 7 and 9). but also the major steric and electronic differences between CO and NAPHOS ligands. however.C. The Rh-NAPHOS system promotes the formation of linear aldehydes 5a–5c (formyl group in ␥-position) in near 95% regioselectivity starting from allylbenzenes and branched aldehydes 3a and 3c (formyl group in ␣-position) in near 90% regioselectivity starting from propenylbenzenes.5-cyclooctadiene)rhodium(I)] as a catalyst precursor can be controlled by the nature of phosphorous auxiliary ligands. / Journal of Molecular Catalysis A: Chemical 179 (2002) 133–141 3a is formed as a main product in a 76% regioselectivity and virtually 100% chemoselectivity. runs 6 and 8). Varying the reaction conditions. which chelate almost exclusively to diequatorial sites in five coordinate rhodium complexes.19–22]. it has been observed that the higher the bite angle.and regioselectivity of the hydroformylation of allylbenzenes 1a–1c and propenylbenzenes 2a and 2c using bis[(␮-acetate)(1. However. the presence of two strong donor phosphines in the equatorial plane in Rh-NAPHOS complexes which increases a back donation from rhodium to the equatorial olefin ligand and could change the relative charges on carbon atoms. The results on the hydroformylation of propenylbenzenes obtained in our work show that in this specific case the electronic effects should be more important than steric difference between dppp and NAPHOS. Purely steric explanations based on increasing steric bulk of phosphine ligand were considered and ruled out [21]. however remain so far unraveled [15. such as temperature. As expected. Thus. while the Rh-dppp system gives branched aldehydes 4a–4c (formyl group in ␤-position) in near 70% regioselectivity starting from allylbenzenes. purely electronic arguments also failed to explain satisfactorily the data obtained [22]. On the other hand. thus the consideration of both electronic and steric properties is required to understand the effect. in this case. in the hydroformylation of terminal olefins. Diphosphines with larger bite angles (near 120◦ ). run 5). the opposite effect was observed. should be taken into account to interpret the results of the hydroformylation of propenylbenzenes.

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