Inorganica Chimica Acta 359 (2006) 29732979 www.elsevier.

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Rhodium-diphosphite catalysed hydroformylation of allylbenzene and propenylbenzene derivatives

a,*

` nica, Universitat Rovira i Virgili, Marcel.li Domingo s/n, 43007 Tarragona, Spain mica F sica i Inorga Departament de Qu b ` nica, Universitat Rovira i Virgili, Marcel.li Domingo s/n, 43007 Tarragona, Spain mica Orga Departament de Qu Received 21 November 2005; accepted 11 December 2005 Available online 3 March 2006 Dedicated to Brian James.

Abstract The asymmetric hydroformylation of allylbenzenes and propenylbenzenes is an important tool for obtaining high value intermediates for the pharmaceutical and perfume industry. We have studied these reactions with rhodium-chiral diphosphite systems. The diphosphite ligands 6 and 7 with carbohydrate backbone have high regioselectivities in trans-anethole hydroformylation and moderate ones in estragole hydroformylation. Only low enantioselectivities have been observed in the trans-anethole hydroformylation with the diphosphite 6 based system. 2006 Elsevier B.V. All rights reserved.
Keywords: Hydroformylation; Rhodium; Allylbenzene; Propenylbenzene; Selectivity

1. Introduction The asymmetric hydroformylation reaction is an important tool for synthesizing enantiomerically pure aldehydes. These are important precursors of biologically pure compounds, biodegradable polymers and liquid crystals [13]. On the other hand, the hydroformylation of terpenes makes it possible to produce aldehydes of interest to the perfume industry (Scheme 1) [48]. The hydroformylation of terpenes such as eugenol, safrole and estragol, which are allylbenzenes, and their isomers, isoeugenol, isosafrole and trans-anethole, which are propenylbenzenes (Fig. 1), is interesting for the formation of aldehyde derivatives for the avour industry [8]. Although asymmetric hydroformylation of vinylaromatic compounds has been widely studied [13,9], there are very few studies on the hydroformylation of allylbenzenes and propenylbenzenes [1013].
*

Corresponding author. Tel.: +34 977 559575; fax: +34 977 559563. E-mail address: claver@quimica.urv.net (C. Claver).

The hydroformylation of propenylbenzenes 1 (Scheme 2) makes it possible to synthesize two branched aldehydes 3 and 4, but the isomerization of these olens to the terminal alkenes 2, allylbenzenes, leads to the formation of the branched and linear aldehydes 4 and 5, respectively. The hydroformylation of eugenol 2b and isoeugenol 1b with unmodied rhodium catalysts at very high pressures was studied 25 years ago [10]. A mixture of aldehydes 3, 4 and 5 was obtained (Scheme 2). Temperature was observed to have a strong inuence on the regioselectivity. At low temperature (70 C), the ratio of aldehydes obtained from 1b and from 2b was very dierent, while at 130 C the ratios were closer. This indicates that an isomerization process takes place when the temperature increases, so the process is less selective (Table 1). Kalck et al. [11] reported high selectivities for linear aldehydes 5 when they used the catalytic system [Rh2(lSR)2(CO)2L2] (L: PPh3, P(OMe)3 and P(OPh)3) in the hydroformylation of allylbenzenes (estragole 1c, eugenol 2b, eugenol methyl ether and safrole 3c).

0020-1693/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2005.12.039

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H2 /C O CHO

+ CHO

llimonene CHO H2 /C O CHO H2 /C O

a-pinene

-pinene

H2 /C O OH OH CHO

H 2 /C O OAc OAc CHO

(-) isopulegol

isopulegyl acetate

Scheme 1. Hydroformylation of some terpenes.

HO OMe eugenol

O O safrole

MeO estragole

HO OMe isoeugenol

O O isosafrole

MeO

trans-anethole

Fig. 1. Allylbenzenes and propenylbenzenes.

The asymmetric hydroformylation of trans-anethole 1a r [12] using and estragole 2a was studied by Kolla PtCl2(bdpp) + SnCl2 and [Rh(nbd)Cl]2 + L (L: PPh3 or DIOP) catalytic systems. The regioselectivities with the platinum system were low and were improved when rhodium systems were used. The enantioselectivity observed was low in the hydroformylation of trans-anethole 1a and estragole 2a with both systems. With PtCl2(bdpp) + SnCl2 and DIOP as the ligand, the regioselectivity to the branched aldehdyde 3a was a 53% and with an enantioselectivity of 27.5%. Dos Santos et al. [13] reported the hydroformylation of various allylbenzenes and propenylbenzenes with rhodiumbased systems. They studied the electronic and steric eects of the ligands on the nal distribution of aldehydes and they found that, when monodentate ligands were used, the regioselectivity depended on the basicity of the ligand. Thus, in the hydroformylation of eugenol 2b with the Rh/

P(OPh)3 catalytic system, isomerization to the internal olen was observed, but when the reaction was driven in the presence of PPh3 it was not. However, the use of more basic phosphines, such as P(Cy)3 and P(n-Bu)3, decreased the activity and the regioselectivity in the linear aldehyde. The activity of the less basic ligands is higher because the electron-withdrawing ligands decreased the back-donation to carbon monoxide and thus weakened the binding of the carbonyls. This favours the dissociation of carbon monoxide because it increases the reaction rate [3]. The eect of the basicity of the monodentate ligand on the regioselectivity could be explained by the basicity of the hydride. A basic phosphine leads to an increase in the nucleophilicity of the hydride. Therefore, the interaction of the hydride with the terminal carbon (which bears a more positive fractional charge than the b-carbon) is favoured, leading to trace amounts of branched aldehyde 4a [13]. When diphosphine-based systems (dppe, dppb, BISBI and NAPHOS) were used, the bite angle of the diphosphine and the regioselectivity were related (Table 2). Thus, it can be observed that ligands with big bite angles (BISBI and NAPHOS) aorded the linear aldehyde almost exclusively, while for ligands with small bite angles (dppe, dppp) the regioselectivity for the linear aldehyde decreased dramatically (<40%). This behaviour has been attributed to the coordination mode of these ligands. In the trigonal-bipyramidal rhodium-hydride species, the ligands with small bite angles coordinate in apicalequatorial positions giving more basicity to the hydride (trans to a P ligand) than the diphosphines with major bite angle (around 120) that coordinates in equatorialequatorial mode. The greater basicity of the hydride makes it possible

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*
+ R1 R2 4 H O

*
+ O R1 R2 5 O

R1 OCH3 OH

R2 H OCH3 1a 1b 1c

compound trans-anethol isoeugenol isosafrol 2a 2b 2c

compound estragole eugenol safrole

-OCH2O-

Scheme 2. Hydroformylation of allylbenzene and propenylbenzene.

Table 1 Hydroformylation of isoeugenol 1b and eugenol 2b by [Rh(Cl)(COD)]2a [10] Temperature Substrate 1b 3b (a) 70 80 100 130
a

2b 4b (b) 5 10 45 50 5b (c) 0 0 5 10 3b (a) 0 3 11 41 4b (b) 48 45 37 24 5b (c) 52 52 52 35

95 90 50 40

Reaction conditions: 20 ppm [Rh(Cl)(COD)]2, 600 bar (CO/H2 = 1/1).

Table 2 Hydroformylation of eugenol 2b by [Rh(COD)(OAc)]2/diphosphine systema [13] Diphosphineb dppe dppp dppb BISBI NAPHOS
a

Bite angle ( ) 85 91 98 123 120

Time (h) 24 24 24 7 7

Conv.c (%) 55 74 99 81 90

4 (b) 62 69 34 2 2

5 (c) 38 31 66 98 98

5/4 (c/b) 0.6 0.5 1.9 49.0 49.0

Reaction conditions: substrate (10.0 mmol), [Rh(COD)(OAc)]2 (0.005 mmol), diphosphine (0.20 mmol), benzene (40 ml), 2 Mpa (CO/ H2 = 1/1), 80 C. b dppe:1,2-bis(diphenylphosphino)ethane; dppp:1,3-bis(diphenylphosphino)propane; dppb: 1,4-bis(diphenylphosphino)butane, NAPHOS: 2, 2 0 -bis[(diphenylphosphino)methyl]-1,1 0 -binaphthyl; BISBI: 2,2 0 -bis[(diphenylphosphino)methyl]-1,1 0 -biphenyl. c Determined by GC; hydrogenated substrate is detected in trace amounts.

to obtain greater amounts of the branched aldehyde because of the favoured interaction of the hydride with the terminal carbon. This eect has already been studied

in the hydroformylation of 1-alkenes [14]. Although it is usually accepted that the inuence of the bite angle on the regioselectivity is related to electronic eects, steric factors cannot be ignored. In spite of the numerous studies on the correlation between the bite angle and the regioselectivity, this relationship has yet to be claried [1519]. It is known that the hydroformylation rate of propenylbenzenes is lower than that of allylbenzenes. The rate-determining step in the hydroformylation reaction is usually the coordination of the alkene, and because the internal alkenes are more hindered their coordination is more disfavoured than the terminal alkenes. With unmodied rhodium systems, the regioselectivities depend on temperature and pressure. At high temperature, isomerization increases because b-elimination is favoured [3]. The increase in the partial pressure of carbon monoxide (CO/H2 = 2/1) led to a slight decrease in the activity and did not aect the regioselectivity. As in the case of allylbenzenes, when diphosphine ligands were studied, the nature of the ligand was also seen to depend on the regioselectivity. Thus, NAPHOS with a larger bite angle provided regioselectivities over 90% to the a-aldehyde (3), while dppp showed regioselectivities around 70% in this isomer. Chiral diphosphite ligands have been widely used in asymmetric hydroformylation and they have shown good activities, regioselectivities and enantioselectivities [9]. However, they have not been used in the hydroformylation of allylbenzenes and propenylbenzenes. In this context, we decided to study the hydroformylation of trans-anethole 1a and estragole 2a with a rhodium catalyst modied with diphosphite chiral ligands 6 [20] and 7 [21] (Fig. 2). Diphosphite ligand 6 has C1-symmetry and three carbons between the phosphorus moieties, which forms an 8-membered chelate ring. However, ligand 7 has C2-symmetry

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O O P O O

O P O O O O TBDPSO O O P O O 6 7

O O P O OTBDPS O = O

But

tB u

But R1 = t Bu

OO

tBu

R2 = t Bu

Fig. 2. Diphosphite chiral ligands with a carbohydrate backbone.

with two carbons in the bridge between the phosphorus atoms, which forms a 7-membered chelate ring. These ligands have been previously used in the rhodium-catalysed hydroformylation of styrene [20,21] and have shown high regioselectivities to branched aldehyde and moderate enantioselectivities (95% and 40%(S), respectively, for ligand 6, and 97% and 46%(S), respectively, for ligand 7). It is to be expected that the higher substitution of the double bond in trans-anethole will produce a change in the regioselectivity and stereoselectivity of the process. 2. Results and discussion 2.1. Asymmetric hydroformylation of trans-anethole 1a (propenylbenzene) We studied the hydroformylation of trans-anethole 1a with a rhodium-based system (Scheme 2). Unlike styrene, the model substrate in asymmetric hydroformylation, this substrate is an internal olen. The trans-anethole 1a needs more drastic conditions of reaction than the styrene, and

two branched aldehydes 3a and 4a could be obtained with the formyl group in a- or b-positions, respectively. If 1a isomerizes to estragole 2a, the hydroformylation of 2a will lead to the formation of two aldehydes: the branched b-isomer 4a and the linear aldehyde 5a. The trans-anethole was hydroformylated by an in situ formed catalyst, by adding diphosphite ligands 6 or 7 to a solution of the rhodium precursor ([Rh(acac)(CO)2]). The results are summarized in Table 3. The Rh/6 catalytic system gives a higher conversion than when no ligand or PPh3 was used, while the selectivity in isomer 3a was lower than in the presence of PPh3 and higher than in the absence of ligand (Table 3, entries 1, 2, 3). Increasing the reaction temperature from 60 to 80 C (Table 3, entry 3 versus 4) produces no signicant changes in the isomerization, a small increase in the conversion but a considerable decrease in the selectivity of 3a. Similar behaviour was observed by Dos Santos et al. [13] in the hydroformylation of propenylbenzenes with an unmodied rhodium catalyst. This eect is general in hydroformylation and has been observed in other substrates. It is a consequence

Table 3 Hydroformylation of trans-anethole 1a with the Rh/6 and Rh/7 catalytic systema
O H * H2 /C O MeO 1a Rh Me O 3a * + Me O 4a H O + MeO 5a
b

H O

Entry

Rh/L/S

T (C)

P CO (atm)

P H2 (atm)

% Conv. ald.

% Isom.

Product distribution (%)b 3a (a) 4a (b) 30 <1 19 31 16 30 14 33 22 5a (c) 2 0 <1 3 <1 2 <1 3 3

%ee 3a (a)b

%ee 4a (b)b

1 2 3 4 5 6 7 8 9
a b

1//200 1/4/200 1/1/200 1/1/444 1/2/200 1/1/200 1/1/200 1/1/200 1/2/200

PPh3 6 6 6 6 6 7 7

60 60 60 80 60 60 60 60 60

20 20 20 20 20 10 20 20 20

20 20 20 20 20 20 40 20 20

56 18 87 92 84 70 96 79 39

5 6 2 4 <1 2 <1 8 5

68 >99 81 66 84 68 86 65 75

0 0 0 0 8 0 0

0 0 0 0 15 0 0

trans-Anethole 1.8 mmol, [Rh(acac)(CO)2] 0.009 mmol, 10 ml toluene, reaction time: 24 h. % Determined by GC hydrogenated substrate is detected in trace amounts.

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of the increase in the b-elimination rate when the temperature increases [3]. The comparison of the results of the Rh/6 system and the unmodied rhodium system, at the same conditions, revealed that only one equivalent of the ligand was required to maintain the active species coordinated to the ligand. When the rhodium/diphosphite ratio was 1 or 2 (Table 3, entries 3 and 5) the regioselectivity to branched aldehyde 3a was similar (81% and 84%), while with unmodied rhodium system the regioselectivity is 68% to the branched aldehyde 3a (Table 3, entry 1). A decrease in CO partial pressure led to a decrease in the activity and regioselectivity in a-isomer 3a (Table 3, entry 6 versus entry 3). At lower pressures, the CO insertion rate decreases and the b-elimination is favoured, which leads to a higher isomerization [3]. The increase in the hydrogen partial pressure signicantly aected the conversion but did not aect the regioselectivity of the reaction (Table 3, entry 7). This suggests that hydrogenolysis is the rate-determining step. Fig. 3 shows the composition of the reaction mixture during the hydroformylation with the rhodium-diphosphite 6 system. After an induction period of 1 h, the formation of aldehydes increases rapidly with a TOF = 17.2 h1 (60 C). This TOF is lower than for the same system in styrene hydroformylation TOF = 53 h1 (40 C) P = 25 bar [22]. The isomerization is very low (<1%), and the estragole formed is rapidly hydroformylated. We also studied the hydroformylation of trans-anethole 1a using the Rh/7 catalytic system (Table 3, entries 8 and 9). In this case, unlike the rhodium-diphosphite ligand 6 system described above, 2 equiv. of the diphosphite ligand were necessary to maintain the active species coordinated to ligand. When the rhodium/ligand ratio is 1/1 (Table 3, entry 8), the regioselectivity is the same as for the unmod-

ied rhodium system (Table 3, entry 1). In fact when the rhodium/ligand ratio is 1/2 (Table 3, entry 9), the regioselectivity to the a-isomer 3a increases and the activity is lower than when it is 1/1. This indicates that intermediate rhodium-diphosphite ligand 7 species are less stable than with ligand 6 and require more equivalents of ligands to maintain these species with the ligand coordinated. The results of the two diphosphite ligands, obtained in the same conditions, show that the catalyst based on ligand 6 is more selective in a-aldehyde 3a than diphosphite 7 (Table 3, entry 5 versus 9). This could be attributed to the nature of ligand 6, which forms an 8-membered chelate ring. Ligand 7, on the other hand, forms a 7-membered chelate ring. This correlation has also been observed in the hydroformylation of 1a with diphosphine ligands [13] and it has been explained above. 2.2. Asymmetric hydroformylation of estragole 2a (allylbenzene) Next, we carried out the asymmetric hydroformylation of estragole 2a. The results are summarized in Table 4. The conditions are the same as those employed for the hydroformylation of trans-anethole 1a. In this case, at least 4 equiv. of ligand were required to prevent the formation of unmodied rhodium species, which are more active but less regioselective. When the rhodium/ligand ratio increases from Rh/L 1/1 to 1/4 (Table 4, entries 24), the regioselectivity to the b-aldehyde 4a and caldehyde 5a increases. The comparison between the catalytic systems Rh/PPh3 and Rh/6 showed that with ligand PPh3, the activity was lower and the regioselectivities were very similar (Table 3, entries 1 and 4). The lower activity of the PPh3 ligand is attributed to the fact that the basicity of this ligand is

100

80

60

40

20

0 0 5
estragole 2a

10
trans-anetol 1a

15
-ald 3a

20
-ald 4a

25
-ald 5a

Fig. 3. Product distribution versus reaction time diagram of the hydroformylation of trans-anethole 1a with diphosphite 6-rhodium catalyst (temp: 60 C, pressure 35 atm CO/H2 1:1).

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Table 4 Hydroformylation of estragole 2a with the catalytic system Rh/6a

H O

Entry

Rh/L/S

T (C)

P CO (atm)

P H2 (atm)

% Conv. ald.

% Isom.

Product distribution (%)b 3a (a) 4a (b) 50 31 36 47 28 5a (c) 50 24 39 53 25

%ee 3a (a)b

%ee 4a (b)b

1 2 3 4 5
a b

1/4/200 1/1/200 1/2/200 1/4/200 1/2/1000

PPh3 6 6 6 6

60 60 60 60 60

20 20 20 20 20

20 20 20 20 20

53 83 94 86 87

24 6.6 1.5 6.1 9.2

<1 45 25 0 47

0 0 0 0

0 0 0 0

Estragole 1.8 mmol, [Rh(acac)(CO)2] 0.009 mmol, 10 ml toluene, reaction time: 24 h. % Determined by GC hydrogenated substrate is detected in trace amounts.

greater than that of the diphosphite ligands. Greater basicity disfavours the dissociation of carbon monoxide and leads to a less active catalyst. The similar regioselectivities shown by these two dierent systems, Rh/PPh3 and Rh/6, are unexpected if we consider the results reported in the literature. The Rh/PPh3 system showed high regioselectivities for linear aldehydes in the hydroformylation of propenylbenzenes [13]. One explanation for this could be the excess of ligand used. Whereas we used a Rh/L ratio of 1/4 in the study mentioned above, the other results were obtained after using an Rh/L ratio of 1/20 and the regioselectivity to the linear aldehyde 5a was nearly 70%. We also observed that when the rhodium/substrate ratio increased from 1:200 to 1:1000 (Table 4, entry 3 and 5), the regioselectivity to the c-isomer 5a was lower, indicating that the presence of more substrate led to more isomerization. 3. Conclusions The use of rhodium-diphosphite based systems in the hydroformylation of trans-anethole 1a and estragole 2a has not been reported before. In this study, rhodiumdiphosphite system 6 was used in the hydroformylation of trans-anethole 1a and led to high selectivities on aldehyde 3a (as high as 86%) under mild conditions (60 C, 40 bar). This is not so dierent from the diphosphine ligands used before which aorded up to 93% of aldehyde 3a with BISBI ligand. We also observed that our diphosphite 6 based system is more active in this reaction than phosphine ligands in similar reaction conditions. When rhodium-diphosphite 7 was used in the trans-anethole 1a hydroformylation, the regioselectivity was lower than when diphosphite 6 was used. We attributed this to the formation of a 7-membered chelate ring of diphosphite 7 when it coordinates to the rhodium. On the other

hand, in the hydroformylation of this substrate new chiral centres (in aldehydes 3a and 4a) are formed by the introduction of formyl groups. We also studied the asymmetric induction of the two diphosphite chiral ligands 6 and 7 in this reaction. We only observed low enantioselectivities in the case of diphosphite 6 in trans-anethole 1a hydroformylation. In the hydroformylation of estragole 2a, we used rhodium-diphosphite ligand 6. In this case, regioselectivities on the branched aldehyde 4a were low (47% of 4a and 53% of 5a) when excess of ligand was added. We also investigated the enantioselectivity but we did not observe asymmetric induction in the conditions studied. 4. Experimental 4.1. General methods All syntheses were performed by standard Schlenk techniques under a nitrogen or argon atmosphere. Diphosphites 6 and 7 were prepared by previously described methods [20,21,23]. The Solvents were puried by standard procedures. All the other reagents were used as commercially available. Gas chromatographic analyses were run on a HewlettPackard HP 5890A instrument (split/splitless injector, J&W Scientic, HP-5, 25 m column, internal diameter 0.25 mm, lm thickness 0.33 mm, carrier gas: 150 kPa Ar, F.I.D. detector) equipped with a Hewlett Packard HP3396 series II integrator. Hydroformylation reactions were carried out in a Parr 450 ml multiple reaction vessel autoclave. Enantiomeric excesses were measured after oxidation of the aldehydes to the corresponding carboxylic acids on a HewlettPackard HP 5890A gas chromatograph (split/splitless injector, J&W Scientic, Supelco b-DEX 110 (30 m. column, internal diameter 0.25 mm., carrier gas: 100 kPa He, F.I.D. detector)).

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4.2. Hydroformylation experiments The catalytic precursors were prepared in a multiple reaction vessel autoclave in a glovebox, by adding the ligands to a solution of [Rh(acac)(CO)2] (0.009 mmol) in toluene (10 ml). Then, the substrate was added. After pressurizing to the desired pressure with syngas and heating the autoclave to the reaction temperature, the reaction mixture was stirred for 24 h. Then, the autoclave was cooled to room temperature and depressurized. The reaction mixture was analysed by gas chromatography. The aldehydes obtained from the hydroformylation were oxidized to carboxylic acids to determine the enantiomeric excess. Acknowledgements n y Cultura We thank the Spanish Ministerio de Educacio and the Generalitat de Catalunya (DURSI) for their nancial support (CTQ2004-04412/BQU and 2001SGR-00316). We also thank CYTED (Red VD and Project V9Iberoamericano). We are also very much indebted to Prof. J. Carles `noma de Bar n and to Laura Crespi, Universitat Auto Bayo celona, for their helpful comments and suggestions. We also acknowledge the support of the Departament dUni i del Fons versitats, Recerca i Societat de la Informacio Social Europeu for a FPI Grant (R.A.). References
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