Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations

Article abstract of DOI:10.1039/c8cc01190g

Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.

Full text of DOI:10.1039/c8cc01190g

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Regioselectivity Inversion Tuned by Iron(III) Salts in Palladium-
Catalyzed Carbonylations†
Zijun Huang, ad Yazhe Cheng,a Xipeng Chen,a Hui-Fang Wang,*b Chen-Xia Du,c and Yuehui Li*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
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bonds.7 In both works, it was shown that catalyst ligands
Impactful regioselectivity control is crucial for cost-effective
chemical synthesis. By using cheap and abundant iron(III) salts, the
hydroxycarbonylations of both aromatic and aliphatic alkenes were
significantly enhanced in both reactivity and selectivity (iso/n or
determine regioselectivities via the hydropalladation step.
In spite of these improvements based on elegant design of
ligands and catalysts, carbonylation procedures often suffer
from drawbacks due to the use of large amounts of strong
Brønsted acids (e.g. hydrochloride, methanesulfonic acid, etc).
Alternatively, Lewis acids are utilized as co-catalysts in
carbonylation reactions showing excellent reaction promotion
effect, although not found suitable for hydroxycarbonylation of
olefins.8,9
n/iso up to
> 99:1). Moreover, Pd-catalyzed carbonylation
selectivity can be switched from branched to linear by using
different Fe(III) salts. In addition, similar results were obtained for
the carbonylation of secondary alcohols.
Carbonylation is an important route for the preparation of
carbonyl compounds providing high regioselectivity essential
for cost-effective chemical synthesis. Carbonylation of alkenes
or alcohols to generate carboxylic acids represents
a
straightforward and atom-efficient methods for drug and fine
chemical synthesis.1-3 In particular, the regioselective
hydroxycarbonylation of terminal alkenes could yield branched
(iso) carboxylic acids (e.g. 2-arylpropionic acid) as core motifs
for non-steroidal drugs, and linear (n) carboxylic acids (e.g.
hydrocinnamic acid) as entities for specialty chemicals.4 Hence,
the discovery of catalytic systems which can conveniently afford
both branched and linear carboxylic acids is highly desirable. In
general, ligand design and development dominates in the
research and innovation to address this challenge.5 Recently,
the research groups of Beller6a and Alper6b explored the ligand-
tuned regioselectivity inversion in carbonylations of C=C
Scheme 1. Fe(III) salts effect in carbonylation reaction.
Despite the frequent usage of Fe(III) salts Lewis acids in
organic synthesis10 and the efforts to develop iron (co-
)catalyzed carbonylations,11 they are conventionally considered
as “inappropriate” co-catalysts for carbonylations due to their
high acidity, sensitivity to water and their oxidizing ability on
olefin substrates.12 However, such drawbacks may be beneficial
for carbonylative generation of carboxylic acids in the presence
of water (Scheme 1), considering the following: (1) the fast
complexation with water leads to Fe(III) aquo cations with
enhanced acidity of the coordinated H2O moieties;13 (2) the
concentration of active Pd(II) species increases via oxidation of
Pd(0) by Fe(III);14 (3) the Fe(III)-hydrolysis equilibrium controls
protons release;15 (4) the availability of vast variety of Fe(III)
salts allows for screening to achieve regioselectivity inversion.
a.State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research
Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of
Sciences, Lanzhou 730000, P. R. China. E-mail:yhli@licp.cas.cn.
b.State and Local Joint Engineering Laboratory for Novel Functional Polymeric
Materials, College of Chemistry, Chemical Engineering and Materials Science,
Soochow University, Suzhou 215123, P. R. China. E-mail: wanghf@suda.edu.cn
c. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou
450001, P. R. China.
Herein we report the first example of Fe(III)-promoters for an
efficient Pd-catalyzed carbonylation of both alkenes and
alcohols, and regioselective preparation of branched and linear
d.University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
†Electronic Supplementary Information (ESI) available: Experimental procedures,
screening of the reaction parameters, spectroscopic data of all products,
computational details. See DOI: 10.1039/x0xx00000x
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carboxylic acids. Furthermore, the regioselectivity was Therefore, it suggested that Fe(III) salts have participated as a
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remarkably inverted by conveniently changing the Fe(III) salt whole in the promotion of the catalytic pDroOcI:e1s0s.1.039/C8CC01190G
additive.
Table 2. Palladium/FeCl3-catalyzed hydroxycarbonylation of alkenesa
Initially, the hydroxycarbonylation of styrene was studied in
the presence of Pd(OAc)2 and the inexpensive ligand PPh3. The
reaction has not occurred without co-catalyst (Table 1, entry
1).16 Subsequently, the screening of more than 20 Lewis acids
(salts of Fe, Al, Zn, Cu, etc) was attempted.17 To our delight, the
use of FeCl3 exclusively led to the branched product 2-phenyl
propionic acid 2a in 96% yields. Specifically, 2 mol% of FeCl3 is
need to have the active Pd-H species formed efficiently. This
outcome is superior to all the tested Brønsted acids (e.g. HCl,
TsOH, etc) and other Lewis acids (e.g. CuCl2) on both yield and
regioselectivity (Table 1, entries 2-5; Table S3). Overall, the use
of polar solvents such as dioxane or THF was critical for both
reactivity and selectivity, while bidentate phosphine ligands
favored the linear product, albeit having low yields (Tables S2,
S4-6).
Table 1. Catalytic hydroxycarbonylation of styrenea
Entry
[Pd]
co-catalyst/x
Yield/%
iso/n
aReaction conditions: 1 (1 mmol), CO (50 bar), H2O (2 mmol),
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
PdCl2
-
1
2
0
--
Pd(OAc)2 (0.01 mmol), PPh3 (0.03 mmol), FeCl3 (0.02 mmol), 80 °C;
FeCl3/2
HCl/2
96
90
36
35
45
18
82
27
75
99
50
87
> 99/1
92/8
1
b
isolated yield; iso/n ratio determined by H NMR analysis. 100 °C.
cPd(OAc)2 (0.02 mmol), PPh3 (0.06 mmol), FeCl3 (0.04 mmol), 120 °C.
diso/n Ratio and yield determined by GC. eHCl (0.06mmol; 1,4-
dioxane solution) was used instead of FeCl3.
3
4b
HOTf/2
CuCl2/2
Fe(OMs)3/5
Fe(OTs)3/5
Fe(OTf)3/5
Al(OTf)3/5
-
24/76
> 99/1
27/73
39/61
15/85
32/68
99/1
5
6b
7b
8b
9b
10
11
12b
13b
We subsequently explored the substrate scope in the
presence of FeCl3 for the hydroxycarbonylation of olefins (Table
2). The meta- or para-substitution on the phenyl ring of styrene
had minimal influence on the reactivity and full conversion was
consistently achieved, with high regioselectivity for branched
products (2a to 2o, iso/n > 97/3; 56–96% yields). For the
reactions of 1i and 1k, lower yields were obtained mainly due
to the polymerization of olefin starting materials (56-64%
yields). Remarkably, the racemic form of Ibuprofen (2l) was
obtained in 92% yield with exclusive branch selectivity
observed. In addition, when electron withdrawing halides (e.g.
ortho-Cl) present in the substrate, lower regioselectivity was
observed (iso/n ratio as 93/7 for 2s). Interestingly, the reaction
of the substrate ortho-F styrene (2r) showed similar high branch
selectivity with substrates containing electron donating groups
PdCl2
FeCl3/2
-
> 99/1
24/76
19/81
Pd(OTf)2
Pd(OTf)2
Fe(OTf)3/5
aReaction conditions: 1a (1.0 mmol), CO (50 bar), H2O (2.0 mmol),
1,4-dioxane (2.0 mL), 80 °C. Yields and iso/n ratios determined by 1H
NMR analysis. bCO (10 bar), H2O (1.0 mmmol), 120 °C. OTf = triflate.
OMs = methanesulfonate. OTs = tosylate.
Screening of different iron salts revealed that non-
coordinating anion containing salts favored the formation of
linear product 3-phenylpropionic acid 3a, with a yield of 82%
and iso/n ratio of 15/85 being obtained by using Fe(OTf)3 (Table
1, entries 6-8).17,18 We also noticed that the water-tolerable
Al(OTf)3 is less efficient compared to Fe(OTf)3 (Table 1, entry 9).
The critical anion effect on regioselectivity was clarified by using
PdCl2 or Pd(OTf)2 as metal precursors. Specifically, chloride and
triflate anions are capable to influence the regioselectivity
favouring the generation of iso and n-isomers, respectively.
Nevertheless, the catalytic activity was significantly improved
by the addition of FeCl3 or Fe(OTf)3 (Table 1, entries 11-13).
(
2p
Notably, the reaction of 3-vinyl pyridine proceeded smoothly
affording 2-pyridyl propionic acid as the only observed product
2t, 73% yield), which is an important moiety in drug
-2q).
(
development.19 Aliphatic olefin substrates were tested and
good reactivity was obtained (2u, 86% yield). The reaction of
terminal aliphatic olefin such as 1-hexene showed little
regioselectivity, whereas internal olefins are suitable substrates
showing moderate regioselectivity. For example, the reaction of
2 | J. Name., 2012, 00, 1-3
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2-octene (E/Z mixture) generated 2-methyloctanoic acid as the found unable to initiate the reaction. In addition, palladium black
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DOI: 10.1039/C8CC01190G
major product (2w: 71% yield, 72% selectivity for 2-position).
formation was not observed when using FeCl3 or Fe(OTf)3 as co-
catalysts. We also found that better results were achieved by using
Fe(III) salts over HCl or HOTf in both reactivity and selectivity. Here,
we expect the oxidizing ability of Fe(III) may be involved in impeding
the tendency of Pd(0) cluster formation associated with catalyst
decomposition to palladium black (redox potential difference
between Fe3+/Fe2+ +0.77 V and Pd2+/Pd0 +0.60 V).21 Furthermore, the
interaction between Fe(III) and Pd(II) compounds could be observed
by the red shift of the signal of Pd(OTf)2 by 5 nm upon addition of
Fe(OTf)3 (Figures S1-2). We also assessed the reaction profiles by
using different acidic additives and clearly Fe(III) salts showed more
efficient promotion effect compared with Brønsted acids (HCl or
HOTf). Moreover, the reactions proceeded at more constant rates
when using Fe(III) salt co-catalyts as shown in Figures S3-4.17
We also performed in situ NMR experiments in d-THF for the
reactions of styrene using 13C-labelled CO (2–5 bar) in the presence
of PdCl2 and Pd(OTf)2, respectively. Pd-H hydride signals (-6.51, -7.42
ppm) were observed for the reaction using Pd(OTf)2 even at 25 °C
(Figure 1, left). The 13C NMR showed Pd-acyl signals for both neutral
(Cl) and cationic (OTf) Pd-systems under heating conditions (Figure
1, right). These results suggest the presence of both active Pd-H and
Pd-acyl species consistent with Pd-H mechanism from literature
reports.5
Table 3. Palladium-catalyzed hydroxycarbonylation of olefins in
the presence of Fe(OTf)3
a
aReaction conditions: 1 (1 mmol), CO (10 bar), H2O (1 mmol),
Pd(OAc)2 (0.01 mmol), PPh3 (0.06 mmol), Fe(OTf)3 (0.05 mmol);
isolated yield; iso/n determined by 1H NMR analysis.
bPd(OTf)2(CH3CN)4 (0.01mmol), PPh3 (0.06 mmol), FeCl3 (0.02 mmol).
cH2O (3 mmol); iso/n determined by GC. dYield determined by GC.
Furthermore, the scale-up ability was tested for the reaction
of styrene (62.4 g styrene) with a substrate-to-catalyst ratio of
60,000. The reaction proceeded smoothly and 2-
phenylpropionic acid was obtained in 40% yield (51%
conversion) in 51.5 hours at 100 °C under 50 bar of CO. This
corresponds to a turnover number (TON) value of 24,000 and
turnover frequency (TOF) of 466 h-1.17 Also, asymmetric catalytic
reactions were investigated in the presence of FeCl3, and
preliminary results showed negligible chiral induction and
excellent branched selectivity with a bisphosphine ligand.20
We also investigated the substrate scope in the presence of
Fe(OTf)3 as co-catalyst (Table 3). n/iso Ratios around 4:1 were
observed for most of the tested aromatic substrates. Moderate
Figure 1. Left: 1H NMR of the reaction using Pd(OTf)2(CH3CN)4-PPh3;
Right: 13C NMR of the reaction using PdCl2 (Red) or Pd(OTf)2(CH3CN)4
(blue). 10 mol% Pd precursor, 5 bar 13CO (initial pressure), room
temperature to 60 °C in d-THF. THF = Tetrahydrofuran.
In order to further clarify the anion effect in this catalytic system,
DFT calculations were carried out on the hydropalladation step,
which is considered to be critical in determining regioselectivity.6
Specifically, the calculated energy barrier for the double bond of
styrene to insert into [L2PdH]Cl is 13.3 kcal/mol by way of producing
the branched product, and is 16.6 kcal/mol for producing the linear
product with solvation effect included (see computational details in
the SI). The result corresponds to an expected regioselectivity close
to > 99/1 (iso/n) according to Arrhenius equation. While for [L2PdH]+
catalyst (corresponding to systems with non-coordinating anion), the
regioselectivity switches to 25/75 (iso/n) based on the calculated
barrier difference by 0.34 kcal/mol (6.26 vs 5.30 kcal/mol).7 Such
calculation result coincides well with the experimentally observed
regioselectivity in Table 1. The calculation reveals that the anion
effect has a pronounced influence on the styrene insertion step,
which is related to the regioselectivity determination.
to good yields were obtained and the lower yields for 3o, 3q, 3x
and 3aa were mainly due to the incomplete conversion with
significant amounts of starting materials recovered. Notably, up
to 99:1 n-selectivity was achieved for ortho-Br or Cl substituted
styrenes (3s
reactions of aliphatic olefins (3w
,
3y). Reasonable selectivity was achieved for
3z 3ac). In particular, for 3w,
,
-
3ab and 3ac, the four possible products were obtained
favouring carbon centers 1 and 2 selectivity at a calculated ratio
of 2:1. The reaction also proceeded well for internal olefin such
as with 2-octene favouring carbon center 1 selectivity (55%).
The hydrolysis of Fe(III) salts in the presence of water will provide
an accommodating “acidic-buffer system” (1.0–1.7 pH) allowing for
critical Pd-H formation.17 In contrast to the high efficiency obtained
by using Fe(III) salts, Fe(II) salts (e.g. FeCl2) with weaker acidity were
The additive effect of iron salts in carbonylation of aryl
ethanols was also investigated (Table 4). We observed similar
performance on promotion and selectivity controls, and the
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Martin, J. Am. Chem. Soc., 2017, 139, 12161. (d) Q. Meng, S.
corresponding acid products were obtained in high yields (75-
91%). Notably, when FeBr3 was used as the promoter, branched
products were generated with 87-96% regioselectivity; and
linear products were obtained with up to 94% regioselectivity in
the presence of Fe(OTs)3.
Wang, G. S. Huff, B. Ko .
̈
nig, J. Am. Chem. Soc., 20V1ie8w, 1Ar4ti0cl,e3O1n9lin8e
5
(a) M. S. Goedheijt, J. N. H. Reek, P. CD. OJ.I:K1a0m.10e3r9,/PC.8CWC.0N11.9M0G.
van Leeuwen, Chem. Commun., 1998, 2431; (b) H. Neumann,
A. Brennführer, M. Beller, Adv. Synth. Catal., 2008, 350, 2437;
(c) S. Jayasree, A. Seayad, R. V. Chaudhari, Org. Lett., 2000, 2,
203; (d) C. Godard, B. K. Muñoz, A. Ruiza, C. Claver, Dalton
Trans., 2008, 853.
J. Liu, Q. Liu, R. Franke, R. Jackstell, M. Beller, J. Am. Chem.
Soc., 2015, 137, 8556; (b) T. Xu, F. Sha, H. Alper, J. Am. Chem.
Soc., 2016, 138, 6629.
Table 4. Palladium-catalyzed carbonylation of alcoholsa
6
7
I. del Río, C. Claver, P. W. N. M. van Leeuwen, Eur. J. Inorg.
Chem., 2001, 2719.
8
9
T. O. Vieira, M. J. Green, H. Alper, Org. Lett., 2006, 8, 6143.
D. B. G. Williams, M. L. Shaw, M. J. Green, C. W. Holzapfel,
Angew. Chem. Int. Ed., 2008, 47, 560.
10 L.-W. Xu, C. G. Xia, X. X. Hu, Chem. Commun., 2003, 2570; (b)
K. Komeyama, T. Morimoto, K. Takaki, Angew. Chem. Int. Ed.,
2006, 45, 2938; (c) K. S. Williamson, T. P. Yoon, J. Am. Chem.
Soc., 2010, 132, 4570; (d) W. Liu, Y. Li, K. Liu, Z. Li, J. Am. Chem.
Soc., 2011, 133, 10756. (e) B. Alcaide, P. Almendros, M. T.
Quirós, Adv. Synth. Catal., 2011, 353, 585. (f) B. Alcaide, P.
Almendros, I. Fernández, T. M. del Campo, T. Naranjo, Adv.
Synth. Catal., 2013, 355, 2681.
a
Reaction conditions: 4 (1.0 mmol), CO (50 bar), H2O (2.0 mmol),
toluene (2.0 mL), 120 °C, 15 h; isolated yields; iso/n ratio determined
by 1H NMR analysis. PTSA = p-Toluenesulfonic acid.
In summary, we have developed the first example of Fe(III)-
promoted Pd-catalyzed carbonylation for the generation of
carboxylic acids, with the regioselectivity tuned by Fe(III) salts.
In the presence of cheap and readily available Fe(III) salts,
various aromatic and aliphatic olefins are transformed into the
desired carboxylic acids in good yields with medium to excellent
regioselectivities. The reaction rates observed are commercially
viable. TON up to 24,000 were achieved and with the advantage
11 (a) F. Ungváry, Coordin. Chem. Rev., 2001, 218, 1; (b) C.
Breschi, L. Piparo, P. Pertucci, A. M. Caporusso, G. Vitulli, J.
Organomet. Chem., 2000, 607, 57; (c) A. M. Trzeciak, E.
Mieczynska, J. J. Ziolkowski, Top. Catal., 2000, 11, 461; (d) K.
M. Driller, H. Klein, R. Jackstell, M. Beller, Angew. Chem. Int.
Ed., 2009, 48, 6041.
12 J. Yang, Y. Yuan, Catal. Lett., 2009, 131, 643.
of simply changing the anion of Fe(III) salts, the iso-selectivity 13 (a) Comparative Inorganic Chemistry, Bernard Moody, 3rd
edition, 1991, Edward Arnold, New York. (b) H. Yamamoto,
(Ed.), Lewis Acids in Organic Synthesis, Wiley-VCH, Weinheim,
2000.
(up to > 99/1) was inverted to n-selectivity (up to 99/1).
Preliminary mechanistic studies reveal the crucial anion effect
influence the insertion of olefins to the Pd-H bond.
We are grateful for the financial supports from NSFC
(21633013, 21101109, 21602228), NSF of Jiangsu Province
(BK20160394) and the National Program for Thousand Young
Talents of China.
14 (a) V. V. Potekhin, Russ. J. Gen. Chem., 2007, 77, 1593; (b)
Palladium Catalyzed Oxidation of Hydrocarbons, Henry P. p44,
D. Reidel Publishing Company, Dordrecht. About the role of
palladium colloids in Heck reactions, see: (c) J. G. de Vries,
Dalton Trans., 2006, 421.
15 J. C. M. Flynn, Chem. Rev., 1984, 84, 31.
16 V. V. Grushin, Chem. Rev., 1996, 96, 2011.
17 For details, see the Supporting Information.
18 B. K. Muñoz, E. S. Garcia, C. Godard, E. Zangrando, C. Bo, A.
Ruiz, C. Claver, Eur. J. Inorg. Chem., 2008, 4625.
19 Y. Miyamoto, Y. Banno, T. Yamashita, et al. J. Med. Chem.,
2011, 54, 831.
Conflicts of interest
There are no conflicts to declare.
20 Preliminary trials on Pd(OAc)2/FeCl3-catalyzed asymmetric
hydroxycarbonylation of styrene using (S,S,S)-SKP as the
ligand were performed, and the desired (S)-acid was obtained
in 48% yield and 25% ee with 99% branch regioselectivity.
Notes and references
1
(a) M. Beller, (Ed.) Catalytic Carbonylation Reactions;
Springer: Berlin, 2006; (b) L. Kollär, Modern Carbonylation
Methods; Wiley-VCH: Weinheim, 2008; (c) X.-F. Wu, H.
Neumann, M. Beller, Chem. Rev., 2012, 113, 1; (d) R. Shi, L. Lu,
H. Zhang, B. Chen, Y. Sha, C. Liu, A. Lei, Angew. Chem. Int. Ed.,
2013, 52, 10582; (e) G. Zhang, B. Gao, H. Huang, Angew.
Chem. Int. Ed., 2015, 54, 7657; (f) S. D. Friis, A. T. Lindhardt, T.
Skrydstrup, Acc. Chem. Res., 2016, 49, 594; (g) X. Ren, Z.
Zheng, L. Zhang, Z. Wang, C. Xia, K. Ding, Angew. Chem. Int.
Ed., 2017, 56, 310; (h) V. Hirschbeck, P. H. Gehrtz, I. Fleischer,
J. Am. Chem. Soc., 2016, 138, 16794.
21 The use of FeCl2/PdCl2 system for oxidative hydroaminations,
see: J. Michaux, V. Terrasson, S. Marque, J. Wehbe, D. Prim, J.
M. Campagne, Eur. J. Org. Chem., 2007, 2601.
2
3
4
(a) H. Koch, W. Haaf, Ann., 1958, 618, 25; (b) W. Han, F. Jin, Q.
Zhou, Synthesis, 2015, 47, 1861.
C. Ballatore, D. M. Huryn, A. B. Smith, ChemMedChem, 2013,
8
, 385.
(a) S. M. Korneev, Synthesis
,
2013, 45, 1000. (b) F. Juliá-
Hernández, T. moragas, J. Cornella, R. Martin, Nature, 2017,
545, 84. (c) M. Gaydou, T. Moragas, F. Juliá-Hernández, R.
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TOC
We disclose the Pd-catalyzed carbonylation of alkenes and alcohols, with the regioselectivity
tuned by anion of Fe(III) salts.