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10.1002@anie.200704782
10.1002@anie.200704782
DOI: 10.1002/anie.200704782
Carboxylic Acids
Angewandte
Chemie
3100 www.angewandte.org 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120
Angewandte
Carboxylic Acids in Homogeneous Catalysis Chemie
In organic molecules carboxylic acid groups are among the most From the Contents
common functionalities. Activated derivatives of carboxylic acids have
1. Introduction 3101
long served as versatile connection points in derivatizations and in the
construction of carbon frameworks. In more recent years numerous 2. Reactions via Metal
catalytic transformations have been discovered which have made it Carboxylates 3103
possible for carboxylic acids to be used as building blocks without the
need for additional activation steps. A large number of different 3. Reactions by Extrusion of
Carbon Dioxide 3107
product classes have become accessible from this single functionality
along multifaceted reaction pathways. The frontispiece illustrates an 4. Reactions via Acyl Metal
important reason for this: In the catalytic cycles carbon monoxide gas Species 3112
can be released from acyl metal complexes, and gaseous carbon
5. Reactions with Decarbonylation
dioxide from carboxylate complexes, with different organometallic
of Acyl Metal Species 3114
species being formed in each case. Thus, carboxylic acids can be used
as synthetic equivalents of acyl, aryl, or alkyl halides, as well as or- 6. Summary and Outlook 3117
ganometallic reagents. This review provides an overview of interesting
catalytic transformations of carboxylic acids and a number of deriv-
atives accessible from them in situ. It serves to provide an invitation to The reactivity of carboxylic acids is
complement, refine, and use these new methods in organic synthesis. determined by the two vicinal oxygen
atoms, namely the carbonyl oxygen
atom and that of the acidic hydroxy
1. Introduction group.[1] Under basic conditions the
carboxylic acid group is deprotonated to the resonance-
The compound class of carboxylic acids and the most stabilized carboxylate, which significantly impairs nucleo-
important reactions of the COOH group are known to philic attack at the carbonyl carbon atom. Only under acidic
chemists from as early as the first semester of their studies.[1] conditions is substitution of the hydroxy group possible, for
Carboxylic acids are commercially available in a large example, in esterifications. Under basic conditions nucleo-
structural variety. They are easy to store, simple to handle, philic substitution at the carbonyl carbon atom by the
and when necessary, are accessible preparatively by means of addition–elimination mechanism is, on the other hand,
a large number of well-established methods. For example, possible only when the hydroxy group is replaced by a non-
aromatic carboxylate groups can be produced by the oxida- proton-active leaving group, for example, by dehydration to
tion of side chains of the arene ring, ideally through the use of anhydrides or conversion into acid chlorides or active esters.
atmospheric oxygen as the reagent with formation of water as These fundamental principles also apply to the metal-
the coupling product.[2] This preparative procedure is also catalyzed reactions of carboxylic acids and their derivatives,
suitable for heterocyclic carboxylic acids, although COOH- as illustrated in Scheme 1 where they are divided roughly into
functionalized heterocycles are often more readily available four groups on the basis of the position and polarity of the
than the parent compounds, for instance, when they are bond coupling. In the first reaction mode the O H bond of
synthesized by condensation reactions (e.g. from oxoesters).[3] the free carboxylic acid is cleaved and the carboxylate residue
Synthetic strategies starting from carboxylic acids promise as a whole is linked up with the coupling partner. The
ecological advantages with respect to a number of traditional nucleophilicity of the carboxy oxygen atom allows, for
arene functionalizations that originate from halogenation, example, the reaction with coordinated allyl metal species,
nitration/reduction/diazotization or Friedel–Crafts reactions, as formed, for instance, during the course of allylic substitu-
since these are often waste-intensive and the products are tions or oxidations (see Section 2.1.2). In the presence of
formed to some extent as regioisomers.[1] These sustainability suitable catalysts an insertion into the O H bond is also
aspects also apply to aliphatic carboxylic acids, particularly
when they are accessible from natural sources (renewable raw [*] Prof. Dr. L. J. Gooßen, Dr. N. Rodr.guez
materials) or indirectly by the oxidation of naturally occurring FB Chemie – Organische Chemie
alcohols.[4] Alternatively carboxylic acids may be prepared in TU Kaiserslautern
a simple manner by, for example, the hydrolysis of nitriles, Erwin-Schr:dinger-Strasse Geb. 54
alkylation of malonic esters, or the carbonylation of alkenes 67663 Kaiserslautern (Germany)
Fax: (+ 49) 631-205-3921
or halogenated compounds.[5]
E-mail: goossen@chemie.uni-kl.de
The ready availability of carboxylic acids makes them Homepage: http://www.chemie.uni-kl.de/goossen
extremely promising raw materials for chemical synthesis.
Dr. K. Gooßen
However, usually noncatalytic methods are used, whereas the Bayer HealthCare AG, Strategic Planning Pharma
use of carboxylic acids as substrates in transition-metal MFllerstrasse 178
catalytic methods is currently still more of an exception. 13353 Berlin (Germany)
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 3101
Reviews L. J. Gooßen et al.
observed, however, in reactions with intrinsically nucleophilic As in classical reactions of carboxylic acids, a nucleophilic
coupling partners, for example, in the metal-catalyzed addi- attack at the carbonyl carbon atom with subsequent cleavage
tion of carboxylic acids to alkenes or alkynes with the of the C(O) O bond in catalytic transformations is possible
formation of (enol) esters (Sections 2.1 and 2.2). only when the acid function is activated by substitution of the
The second reaction mode of carboxylic acids comprises O H group. Such activated carboxylic derivatives, including
reactions in which metal carboxylates are formed initially, acid chlorides, anhydrides, active esters, and even a few
then converted into organometallic compounds with the amides and thioesters, react to form acyl complexes, for
extrusion of CO2. This decarboxylation step is usually highly example, with Pd and Rh complexes under oxidative addition
endothermic and only with difficulty can be directed into and can thus be made available for catalytic acylation. This
further catalytic transformations. Even the long-known pro- third reaction mode forms the basis, amongst others, of the
todecarboxylation of aromatic carboxylic acids to the corre- reduction of carboxylic acids to aldehydes, wherein the
sponding arenes requires a transition-metal mediator such as carboxylic acids are converted into anhydrides in situ with
mercury, silver, or copper, usually in stoichiometric amounts pivaloyl anhydride, which are then hydrogenated to the
and at high temperatures. Only in recent years have catalytic aldehydes in the presence of Pd catalysts (Section 4.1). Pd-
variants of this reaction been developed (Section 3.1). catalyzed cross-couplings of carboxylic acids with boronic
Even more valuable for synthesis are reactions in which acids in the presence of different activating reagents follow
carboxylic acids are coupled with other substrates after the same reaction principle (Section 4.2).
decarboxylation. One of the few examples of this is a biaryl In the fourth and last reaction mode the tendency of acyl
synthesis in which aryl nucleophiles generated by the metal complexes, accessible by oxidative addition of activated
decarboxylation of aromatic carboxylic acids are coupled carboxylic acid derivatives to metal catalysts, to decarbon-
with haloarenes on a Pd catalyst (Section 3.2). Following the ylate with the formation of alkyl or aryl metal species is
same mode of reaction carboxylic acids can also react like exploited. In this way organometallic species are formed from
haloarenes (Sections 3.3 and 3.4), namely when the inter- carboxylic acids, just as they are formed by the oxidative
mediate aryl nucleophiles undergo umpolung to carbon addition of haloarenes to metal complexes in the initiating
electrophiles on the metal catalyst before the coupling step. step of many catalytic transformations. Hence, aromatic
This is observed, for example, in a current variant of the Heck carboxylic acids can be converted into vinyl arenes with
reaction, in which carboxylic acids are coupled to vinyl arenes alkenes in Heck reactions (Section 5.2) or coupled to biaryls
with alkenes in the presence of a palladium catalyst and AgI. with boronic acids (Section 5.3).
Lukas J. Gooßen studied chemistry at the Nuria Rodr8guez was born in 1978 in Valen-
University of Bielefeld and the University of cia (Spain). After completion of her chemis-
Michigan. He received his degree in chemis- try studies at the University of Valencia she
try working with Prof. K. P. C. Vollhardt and gained her doctorate in the group Prof. G.
his doctorate in 1997 with Prof. W. A. Asensio and M. Medio-Simon working on
Herrmann at the TU M-nchen. After a palladium-catalyzed cross-couplings with
postdoctoral fellowship with Prof. K. B. participation of an sp3-hybridized carbon
Sharpless and a position as laboratory head center in the a-position to a sulfinyl group.
at Bayer AG he gained his habilitation with Sponsored by a Humboldt Fellowship, she
Prof. M. T. Reetz at the MPI f-r Kohlenfor- has carried out research in the group of Prof.
schung. As Heisenberg Fellow he worked at Gooßen as a postdoctoral fellow since 2006.
the RWTH Aachen until he took up his The emphasis of her work is the develop-
current position in 2005 as Professor of ment of decarboxylative cross-coupling reac-
Organic Chemistry at the TU Kaiserslautern. He is working on the tions.
development of sustainable catalytic transformations.
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Carboxylic Acids in Homogeneous Catalysis Chemie
A sequence of oxidative addition and decarbonylation can reaction conditions could be permitted with the softer metals.
also be carried out successfully with alkyl carboxylic anhy- Unfortunately toxic mercury salts have long been the only
drides on Pd catalysts. If the alkyl metal species thus formed compounds of this type known to facilitate the addition
possess b-hydrogen atoms, alkenes shortened by one carbon reaction in the desired manner.[8] The difficulty in the use of
atom are released by b-hydride elimination (Section 5.1). This transition-metal catalysts is that for many substrates their
Pd-catalyzed decarbonylation of active carboxylic acids is alkyl complexes tend towards b-hydride elimination, so that
thus synthetically equivalent to hydrogen halide elimination the planned redox-neutral catalytic cycle is only too easily
from haloalkanes. diverted into a Wacker-type oxidative process (Section 2.2;
In this review current developments in the area of Scheme 3).[9]
transition-metal catalysis are presented in which carboxylic
acid derivatives function as substrates. Perspectives are
discussed which could be opened up by these conversions in
organic synthesis. In view of the large variety of interesting
reactions, a choice had to be made about which ones to cover.
The main emphasis lies in recently published catalytic trans-
formations that start out either from the carboxylic acids
themselves, or from derivatives that are accessible under mild
conditions. Catalytic reactions of acyl chlorides are men-
tioned only as exceptions, for example, when they serve as a
basis for the development of such reactions. The extensive
literature on the addition of carboxylic acids to multiple
bonds is only briefly presented so as to avoid overlap with Scheme 3. Mechanism of the transition-metal-catalyzed hydroacyloxyla-
tion.
current review articles.
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3103
Reviews L. J. Gooßen et al.
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Angewandte
Carboxylic Acids in Homogeneous Catalysis Chemie
production of vinyl acetate (Scheme 9).[20] This reaction was been used mainly on unsubstituted cyclic systems.[30] Only a
originally carried out in the liquid phase with a PdCl2/NaOAc/ few examples of this reaction type are shown in Scheme 12, as
CuCl2 catalyst, and was later superseded by a reaction it has been comprehensively treated in recent review arti-
procedure on a Pd/Au heterogeneous catalyst in the gas cles.[31]
phase.[21]
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3105
Reviews L. J. Gooßen et al.
Scheme 16. Current ligands for the asymmetric acyloxylation of cyclo- Scheme 17. Ru-catalyzed Markovnikov-selective addition of carboxylic
hexene. acids to alkynes; cot = cyclooctatrienyl.
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Carboxylic Acids in Homogeneous Catalysis Chemie
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3107
Reviews L. J. Gooßen et al.
of carboxylic acids, is long established in organic synthesis.[60] amounts of copper.[70] A species formed from copper oxide
It is particularly useful for cases in which there is a need to and 4,7-diphenyl-1,10-phenanthroline in a mixture of N-
remove a carboxylic group that is still present in the molecule methyl-2-pyrrolidone (NMP) and quinoline functions as the
after a malonic ester or heterocycle synthesis. While highly catalyst (Scheme 24). The reactions are mild enough to
activated carboxylic acids, for example, b-oxoacids, diphenyl-
acetic acids, or polyfluorobenzoic acids, are also readily
decarboxylated in the absence of metals, the release of CO2
from most other carboxylic acids requires the addition of a
transition-metal mediator, generally a copper, silver, or
mercury salt (Scheme 22). Usually this mediator is added in
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Angewandte
Carboxylic Acids in Homogeneous Catalysis Chemie
iodobenzene, some 2-nitrobiphenyl is also formed, presum- protodecarboxylation (Scheme 23). It is assumed that the
ably through a combination of decarboxylation and Ullmann copper species a first coordinates to the carboxylate oxygen
coupling.[62] However, the drastic conditions and the general atom and then inserts into the C C(O) bond via the aryl p-
limitations of crossed Ullmann couplings prevented an system with extrusion of CO2 and the formation of an aryl–Cu
extension of this procedure to a preparatively useful synthesis species (c). At the same time the haloarene adds oxidatively
of unsymmetrical biaryls. Only with the combination of a to a coordinatively unsaturated Pd0 species d. As in a classical
copper or silver decarboxylation catalyst with the classical cross-coupling, a transmetalation then folllows in which the
cross-coupling metal palladium were we successful in the aryl group is transferred from the copper center to the
realization of this transformation (Scheme 27). palladium center (f) with the release of copper halide. The
In the original reaction variant o-nitrobenzoic acid is unsymmetrical biaryl is released by reductive elimination,
initially converted into a particularly reactive CuII salt by the thereby closing the palladium catalytic cycle. To be able to run
reaction with basic copper(II) carbonate and potassium the reaction catalytically with respect to copper, a salt
fluoride with the removal of water that is formed. Decarbox- exchange between fresh potassium carboxylate and the
ylation then affords an aryl copper species at only 120 8C copper halide a is all that is necessary, but this is hampered
which couples with a series of bromoarenes in the presence of by the high affinity of halides for copper ions. In the
2 mol % [Pd(acac)2] and 6 mol % PiPrPh2 in NMP in high alternative Ag/Pd system a reduction in the amount of
yields (Scheme 25). This first version of a decarboxylative silver appears to be hardly feasible in view of the considerable
stability of silver(I) halides.
A second reaction variant has already been developed for
the Cu/Pd system in which not only palladium but also copper
is used in catalytic amounts (Scheme 27).[72] In this variant, o-
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Carboxylic Acids in Homogeneous Catalysis Chemie
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Carboxylic Acids in Homogeneous Catalysis Chemie
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3113
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Scheme 42. Pivalic anhydride one-pot reaction for the coupling of substrates (Scheme 45).[103] The advantage here is that the
carboxylic acids with boronic acids. slightly higher reactivity of this substrate allows the use of a
more robust catalyst system comprising Pd(OAc)2 and PPh3.
A similar catalyst is also used in the synthesis of ketones from
One problem with the original procedure comes from the mixed carboxylic acid/phosphoric acid anhydrides.[104] The
competitive dehydration of a number of boronic acids to high acidity of perfluorocarboxylic acids also allows an
boroxines, as the latter can only be coupled slowly under the analogous Pd-catalyzed synthesis of perfluoroalkyl ketones
reaction conditions. In the reaction variant introduced sub- from their phenyl esters and arylboronic acids.[105]
sequently by Yamamoto et al. somewhat higher temperatures
were used with dioxane as the solvent, which leads to
improved yields with aromatic carboxylic acids.[99] The more
reactive dimethyl dicarbonate can also be used as activating
reagent as an alternative to pivalic anhydride, in which case
only the volatile coupling products CO2 and methanol are
formed (Scheme 43). As was shown in the work of Yamamoto
et al.[100] and ourselves[101] this reaction variant has advantages Scheme 45. Ketone synthesis from o-hydroxypyridyl esters and phenyl-
for more robust substrates, although is not compatible with boronic acid.
quite so large a number of functional groups.
Scheme 43. Dimethyl dicarbonate variants of the ketone synthesis. 5. Reactions with Decarbonylation of Acyl Metal
Species
A more widely applicable reaction variant that is also 5.1. Elimination Reactions with Decarbonylation
compatible with basic heterocycles was developed by our-
selves in which the carboxylic acids are activated with N,N’- The decarbonylation of activated carboxylic acid deriva-
disuccinimidyl carbonate.[102] Here a catalyst system of tives or even aldehydes has been known for a long time from
palladium hexafluoroacetylacetonate and tricyclohexylphos- the work of Tsuji and Ohno,[107] among others. To a certain
phine is used which is stabilized by the addition of solid extent such reactions correspond mechanistically to the
sodium carbonate as a proton trap (Scheme 44). This reaction reversal of frequently used carbonylation processes
is the first example of the use of peptide-coupling reagents in (Scheme 47). Thus, decarbonylations of acid chlorides are
palladium catalysis. induced by the oxidative addition of these compounds to a
Chatani et al. recently introduced a further reaction transition-metal catalyst a with the formation of an acyl metal
variant in which preformed o-hydroxypyridyl esters act as species b; the decarbonylation takes place by migratory
3114 www.angewandte.org 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120
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Carboxylic Acids in Homogeneous Catalysis Chemie
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Reviews L. J. Gooßen et al.
Scheme 54. Proposed mechanism of the Heck reaction starting from As already mentioned in Section 5.1, Ni complexes
esters. formed by the oxidative addition of cyclic anhydrides
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Carboxylic Acids in Homogeneous Catalysis Chemie
decarbonylate particularly, easily forming nickelacycles. based on carboxylic acids. The excellent availability of
Work by Echavarren et al. shows that the reaction of these carboxylic acids from renewable raw material sources,
species with haloalkanes leads to the formation of C(sp3) amongst others, is an important argument to intensify
C(sp3)-coupled cross-coupled products.[118] Since the oxida- research in this area over the next few years.[66] By recombi-
tion state of nickel is raised here from 0 to II, a catalytic nation of elemental steps of the catalytic cycles many further
variant of this reaction is hardly realizable. Rovis et al. chose catalytic transformations may yet be conceived, the synthetic
a complementary approach in which the cyclic anhydrides are potential of which is currently difficult to imagine. Likewise,
reacted with diphenylzinc in the presence of stoichiometric most of the methods presented here are by no means fully
amounts Ni0 complexes (Schema 57).[119] A mixture of simple optimized and offer extensive research possibilities for
catalyst and process developers.
An important target of future research on the (oxidative)
addition reactions of carboxylic acids to multiple bonds is the
efficient control of the chemo-, regio-, and stereoselectivity by
new catalyst systems. In the reactions proceding via acyl metal
complexes, for example, the reduction of carboxylic acids to
aldehydes or the cross-coupling of ketones, it is of particular
interest to increase further the activity of the catalysts and
Scheme 57. Ring opening of cyclic anhydrides with decarbonylation. thus to exploit less activated, more accessible carboxylic acid
cod = cyclooctadienyl. derivatives, such as phenyl or even alkyl esters, as substrates.
This also applies to the methods derived therefrom which
take place with the extrusion of carbon monoxide, for
and decarbonylated cross-coupled products is formed, example, decarbonylative Heck reactions or elimination
although the authors achieved high selectivity in favor of reactions. With a new generation of catalysts able to generate
the decarbonylated product only with the use of stoichio- acyl species under mild conditions from carboxylate deriva-
metric amounts of nickel. Whereas succinic anhydride tives that are accesible from the parent carboxylic acids (e.g.
derivatives react comparably smoothly and stereospecifically, alkyl esters), numerous possibilities arise for the realization of
interesting ring contraction products are formed with deriv- waste-minimized, sustainable synthetic methods.
atives of glutaric anhydride. In the case of decarboxylative cross-couplings it has been
In contrast, our own strategy for the realization of a possible over the last two years to confirm their principal
catalytic decarbonylative cross-coupling is built upon the suitability for transformations which would formerly have
ketone synthesis in Section 4.2. To achieve a cross-coupling by been regarded as hopeless by most chemists. How widely this
decarbonylation the reactivity of the metal catalyst must on new concept may now be applied in synthesis is essentially
the one hand be increased with respect to decarbonylation; dependent upon the extent to which the activity of the
this was achieved by the use of a Rh catalyst instead of a Pd decarboxylation catalysts can be increased. The breadth of
catalyst at a higher reaction temperature. On the other hand applications of the biaryl synthesis is growing continuously,
the reactivity of the organometallic components was inhibited and applications in industry are already being intensively
in that boroxines were used in place of boronic acids, and a investigated. The ketone synthesis from a-oxocarboxylic
nonpolar solvent was used.[120] In this way a variety of acids shows that the potential of this concept already extends
aromatic anhydrides were coupled with different arylborox- beyond the biaryl class of compounds with the current
ines in the presence of a catalyst system of 1.5 mol % catalysts. The lower the temperatures at which future catalyst
[{Rh(ethene)2Cl}2] and 10 mol % potassium fluoride, with generations can decarboxylate carboxylic acid salts to carbon
which selectivities of greater than 10:1 in favor of the nucleophiles are, the broader the spectrum of reaction steps
decarbonylated cross-coupled product were obtained in which can be resultantly combined in situ will be. Examples of
some cases (Scheme 58). this would be further substitution reactions, 1,4-additions to
Michael acceptors, 1,2-additions to multiple bonds, and
nucleophilic opening of stressed rings. It will be exciting to
see how this interesting research area will develop over the
next years.
The versatility of the methods described above foreshad- [1] K. P. C. Vollhardt, N. E. Schore, Organische Chemie, 3rd ed.,
ows the high synthetic potential of catalytic transformations Wiley-VCH, Weinheim, 2000, pp. 893 – 952.
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3117
Reviews L. J. Gooßen et al.
[2] a) J. March in Advanced Organic Chemistry, 4th ed., Wiley, [25] a) K. B. Sharpless, R. F. Lauer, J. Am. Chem. Soc. 1972, 94,
New York, 1992, pp. 1183 – 1184; b) Hudlický in Oxidation in 7154 – 7155; b) K. B. Sharpless, R. F. Lauer, J. Org. Chem. 1974,
Organic Chemistry, American Chemical Society, Washington, 39, 429 – 430.
1990, pp. 105 – 109; c) K. P. C. Vollhardt, N. E. Schore, Organi- [26] M. B. Andrus, J. C. Lashley, Tetrahedron 2002, 58, 845 – 866.
sche Chemie, 3rd ed., Wiley-VCH, Weinheim, 2000, pp. 1081 – [27] a) C. B. Anderson, S. Winstein, J. Org. Chem. 1963, 28, 605 –
1087. 606; b) W. Kitching, Z. Rappoport, S. Winstein, W. G. Young, J.
[3] E. Breitmaier, G. Jung, Organische Chemie II, 1st ed., Georg Am. Chem. Soc. 1966, 88, 2054 – 2055.
Thieme, Stuttgart, New York, 1982, pp. 194 – 245. [28] a) A. Heumann, B. Fkermark, Angew. Chem. 1984, 96, 443 –
[4] Hudlický in Oxidation in Organic Chemistry, American Chem- 444; Angew. Chem. Int. Ed. Engl. 1984, 23, 453 – 454; b) A.
ical Society, Washington, 1990, pp. 127 – 132. Heumann, B. Fkermark, S. Hansson, T. Rein, Org. Synth. 1990,
[5] H. Beyer, W. Walter, Lehrbuch der Organischen Chemie, 24th 68, 109 – 112; c) J. E. McMurry, P. Kočovský, Tetrahedron Lett.
ed., Hirzel, Stuttgart, 2004. 1984, 25, 4187 – 4190.
[6] a) J. March in Advanced Organic Chemistry, 4th ed., Wiley, [29] a) N. Nagato, K. Maki, K. Uematsu, R. Ishioka (Showa Denko),
New York, 1992, pp. 765 – 766; b) J. Guenzet, M. Camps, Jpn. Koka Tokkyo Koho JP 60-32747, 1985; b) T. Yokota, S.
Tetrahedron 1974, 30, 849 – 856; c) J. A. Ballantine, M. Davies, Sakaguchi, Y. Ishii, J. Jpn. Pet. Inst. 2003, 46, 15 – 27.
H. Purnell, M. Rayanakorn, J. M. Thomas, K. J. Williams, J. [30] a) S. E. BystrEm, E. M. Larsson, B. Fkermark, J. Org. Chem.
Chem. Soc. Chem. Commun. 1981, 8 – 9; d) P. E. Peterson, 1990, 55, 5674 – 5675; b) J.-E. BHckvall, S. E. BystrEm, R. E.
E. V. P. Tao, J. Org. Chem. 1964, 29, 2322 – 2325. Nordberg, J. Org. Chem. 1984, 49, 4619 – 4631; c) S. Hansson, A.
[7] E. Negishi in Handbook of Organopalladium Chemistry for Heumann, T. Rein, B. Fkermark, J. Org. Chem. 1990, 55, 975 –
Organic Synthesis Vol. 2 (Eds.: A. de Meijere, J. E. BHckvall, S. 984.
Cacchi, T. Hayashi, Y. Ito, M. Kosugi, S. I. Murahashi, K. [31] E. Negishi in Handbook of Organopalladium Chemistry for
Oshima, Y. Yamamoto), Wiley, New York, 2002, pp. 2141 – Organic Synthesis, Vol. 2 (Eds.: A. de Meijere, J. E. BHckvall, S.
2142. Cacchi, T. Hayashi, Y. Ito, M. Kosugi, S. I. Murahashi, K.
[8] R. C. Larock; B. E. Backer, Tetrahedron Lett. 1988, 29, 905 – Oshima, Y. Yamamoto), Wiley, New York, 2002, pp. 2141 –
908 in Comprehensive Organic Transformations, VCH, New
2150.
York, 1989, pp. 367 – 442.
[32] H. Grennberg, J.-E. BHckwall, Chem. Eur. J. 1998, 4, 1083 –
[9] J. Tsuji in Transition Metal Reagents and Catalysts: Innovations
1089.
in Organic Synthesis, Wiley, Chichester, 2000, pp. 420.
[33] R. C. Larock, T. R. Hightower, J. Org. Chem. 1993, 58, 5298 –
[10] Y. Oe, T. Ohta, Y. Ito, Chem. Commun. 2004, 1620 – 1621.
5300.
[11] C.-G. Yang, N. W. Reich, Z. Shi, C. He, Org. Lett. 2005, 7, 4553 –
[34] a) R. M. Trend, Y. K. Ramtohul, E. M. Ferreira, B. M. Stoltz,
4556.
Angew. Chem. 2003, 115, 2998 – 3001; Angew. Chem. Int. Ed.
[12] J. G. Taylor, N. Whittall, K. K. Hii, Chem. Commun. 2005,
2003, 42, 2892 – 2895; b) Y. Uozumi, K. Kato, T. Hayashi, J. Am.
5103 – 5105.
Chem. Soc. 1997, 119, 5063 – 5064.
[13] K. Komeyama, Y. Mieno, S. Yukawa, T. Morimoto, K. Takaki,
[35] a) A. Heumann, C. Moberg, J. Chem. Soc. Chem. Commun.
Chem. Lett. 2007, 36, 752 – 753.
1988, 1516 – 1519; b) A. Heumann, L. Tottie, C. Moberg, J.
[14] C.-G. Yang, C. He, J. Am. Chem. Soc. 2005, 127, 6966 – 6967.
Chem. Soc. Chem. Commun. 1991, 218 – 220; c) L. Tottie, P.
[15] M. Utsunomiya, M. Kawatsura, J. F. Hartwig, Angew. Chem.
BaeckstrEm, C. Moberg, J. Org. Chem. 1992, 57, 6579 – 6587;
2003, 115, 6045 – 6048; Angew. Chem. Int. Ed. 2003, 42, 5865 –
d) K. NordstrEm, C. Moberg, Tetrahedron Lett. 1994, 35, 7267 –
5868.
7268.
[16] a) M. Beller, J. Seayad, A. Tillack, H. Jiao, Angew. Chem. 2004,
[36] a) M. S. Kharasch, G. Sosnovsky, J. Am. Chem. Soc. 1958, 80,
116, 3448 – 3479; Angew. Chem. Int. Ed. 2004, 43, 3368 – 3398;
756; b) M. S. Kharasch, G. Sosnovsky, N. C. Yang, J. Am. Chem.
b) I. I. Moiseev, M. N. Vargaftik, Coord. Chem. Rev. 2004, 248,
2381 – 2391. Soc. 1959, 81, 5819 – 5824.
[17] A rotation of 608 is necessary if the carboxylic acid attacks from [37] M. B. Andrus, J. C. Lashley, Tetrahedron 2002, 58, 845 – 866.
the outside. If, on the other hand, it is transferred to the alkene [38] J. Eames, M. Watkinson, Angew. Chem. 2001, 113, 3679 – 3683;
outside of the coordination sphere of the palladium atom, as Angew. Chem. Int. Ed. 2001, 40, 3567 – 3571.
the water in the Wacker oxidation of ethene to acetaldehyde, a [39] a) D. B. Denney, R. Napier, A. Cammarata, J. Org. Chem. 1965,
rotation of 1808 is necessary. 30, 3151 – 3153; b) J. Muzart, J. Mol. Catal. 1991, 64, 381 – 384.
[18] I. I. Moiseev, M. N. Vargaftik, Y. K. Syrkin, Dokl. Akad. Nauk [40] A. S. Gokhale, A. B. E. Minidis, A. Pfaltz, Tetrahedron Lett.
SSSR 1960, 133, 377 – 380. 1995, 36, 1831 – 1834.
[19] a) J. Smidt, W. Hafner, R. Jira, J. Sedlmeier, R. Sieber, R. [41] M. B. Andrus, A. B. Argade, X. Chen, M. G. Pamment,
RSttinger, H. Kojer, Angew. Chem. 1959, 71, 176 – 182; b) R. Tetrahedron Lett. 1995, 36, 2945 – 2948.
Jira in Applied Homogeneous Catalysis with Organometallic [42] K. Kawasaki, S. Tsumura, T. Katsuki, Synlett 1995, 1245 – 1246.
Compounds, Vol. 1, 2nd ed. (Eds.: B. Cornils, W. A. Herrmann), [43] a) A. DattaGupta, V. K. Singh, Tetrahedron Lett. 1996, 37,
Wiley-VCH, Weinheim, 2002, pp. 386 – 405. 2633 – 2636; b) A. V. Malkov, M. Bella, V. Langer, P. Kočovský,
[20] a) D. Kumar, M. S. Chen, D. W. Goodman, Catal. Today 2007, Org. Lett. 2000, 2, 3047 – 3049.
123, 77 – 85; b) J. Tsuji, Synthesis 1990, 739 – 749. [44] M. Rotem, Y. Shvo, Organometallics 1983, 2, 1689 – 1691.
[21] a) H. Holzrichter, W. Kroenig, B. Frenz (Bayer), German [45] T. Mitsudo, Y. Hori, Y. Watanabe, J. Org. Chem. 1985, 50, 1566 –
Patent 1185604, 1962 [Chem. Abst. 1964, 60, 11902]; 1568.
b) National Distillers, US Patent 3190912, 1962; British [46] a) H. Doucet, J. HEfer, C. Bruneau, P. H. Dixneuf, J. Chem. Soc.
Patent 976613, 1965 [Chem. Abst. 1965, 62, 14505]. Chem. Commun. 1993, 850 – 851; b) H. Doucet, B. Martin-
[22] T. Izumi, A. Kasahara, Bull. Chem. Soc. Jpn. 1975, 48, 1673 – Vanca, C. Bruneau, P. H. Dixneuf, J. Org. Chem. 1995, 60,
1674. 7247 – 7255.
[23] M. Tanaka, H. Urata, T. Fuchikami, Tetrahedron Lett. 1986, 27, [47] T. Mitsudo, Y. Hori, Y. Yamakawa, Y. Watanabe, J. Org. Chem.
3165 – 3168. 1987, 52, 2230 – 2239.
[24] Z. Rappoport, S. Winstein, W. G. Young, J. Am. Chem. Soc. [48] C. Ruppin, P. H. Dixneuf, Tetrahedron Lett. 1988, 29, 5365 –
1972, 94, 2320 – 2329. 5368.
3118 www.angewandte.org 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120
Angewandte
Carboxylic Acids in Homogeneous Catalysis Chemie
[49] C. Bruneau, P. H. Dixneuf, Angew. Chem. 2006, 118, 2232 – [78] L. J. Gooßen, F. Rudolphi, C. Oppel, N. RodrWguez, Angew.
2260; Angew. Chem. Int. Ed. 2006, 45, 2176 – 2203. Chem. 2008, DOI: 10.1002/ange.200705127; Angew. Chem. Int.
[50] L. J. Gooßen, J. Paetzold, D. Koley, Chem. Commun. 2003, Ed. 2008, DOI: 10.1002/anie.200705127.
706 – 707. [79] a) A. G. Myers, D. Tanaka, M. R. Mannion, J. Am. Chem. Soc.
[51] K. Melis, P. Samulkiewicz, J. Rynkowski, F. Verpoort, Tetrahe- 2002, 124, 11250 – 11251; b) D. Tanaka, S. P. Romeril, A. G.
dron Lett. 2002, 43, 2713 – 2716. Myers, J. Am. Chem. Soc. 2005, 127, 10323 – 10333.
[52] M. Neveux, B. Seiller, F. Hagedorn, C. Bruneau, P. H. Dixneuf, [80] a) R. F. Heck, Org. React. 1982, 27 – 390; b) A. de Meijere, F. E.
J. Organomet. Chem. 1993, 451, 133 – 138. Meyer, Angew. Chem. 1994, 106, 2473 – 2506; Angew. Chem.
[53] B. Seiller, C. Bruneau, P. H. Dixneuf, J. Chem. Soc. Chem. Int. Ed. Engl. 1994, 34, 2379 – 2411; c) I. P. Beletskaya, A. V.
Commun. 1994, 493 – 494. Cheprakov, Chem. Rev. 2000, 100, 3009 – 3066.
[54] a) T. Kondo, A. Tanaka, S. Kotachi, Y. Watanabe, J. Chem. Soc. [81] a) I. Moritani, Y. Fujiwara, Tetrahedron Lett. 1967, 8, 1119 –
Chem. Commun. 1995, 413 – 414; b) L. J. Goossen, J. E. Rau- 1122; b) Y. Fujiwara, I. Moritani, S. Danno, R. Asano, S.
haus, G. Deng, Angew. Chem. 2005, 117, 4110 – 4113; Angew. Teranishi, J. Am. Chem. Soc. 1969, 91, 7166 – 7169; c) M. Tani,
Chem. Int. Ed. 2005, 44, 4042 – 4045; c) L. J. Gooßen, M. S. Sakaguchi, Y. Ishii, J. Org. Chem. 2004, 69, 1221 – 1226.
Blanchot, C. Brinkmann, K. Gooßen, R. Karch, A. Rivas-Nass, [82] I. H. Shinokubo, K. Oshima, J. Am. Chem. Soc. 2003, 125,
J. Org. Chem. 2006, 71, 9506 – 9509. 1484 – 1485.
[55] C. Bruneau, M. Neveux-Duflos, P. H. Dixneuf, Green Chem. [83] C. Peschko, C. Winklhofer, W. Steglich, Chem. Eur. J. 2000, 6,
1999, 183 – 185. 1147 – 1152.
[56] M. T. Reetz, L. J. Gooßen, A. Meiswinkel, J. Paetzold, J. [84] a) H. A. Dieck, R. F. Heck, J. Am. Chem. Soc. 1974, 96, 1133 –
Feldthusen Jensen, Org. Lett. 2003, 5, 3099 – 3101. 1136; b) D. L. Thorn, R. Hoffman, J. Am. Chem. Soc. 1978, 100,
[57] C. Bianchini, A. Meli, M. Peruzzini, F. Zanobini, C. Bruneau, 2079 – 2090; c) R. C. Larock; B. E. Backer, Tetrahedron Lett.
P. H. Dixneuf, Organometallics 1990, 9, 1155 – 1160. 1988, 29, 905 – 908.
[58] H. Nakagawa, Y. Okimoto, S. Sakaguchi, Y. Ishii, Tetrahedron [85] P. Forgione, M. C. Brochu, M. St-Onge, K. H. Thesen, M. D.
Lett. 2003, 44, 103 – 106. Bailey, F. Bilodeau, J. Am. Chem. Soc. 2006, 128, 11350 – 11351.
[59] R. Hua, X. Tian, J. Org. Chem. 2004, 69, 5782 – 5784. [86] a) J. March in Advanced Organic Chemistry, 4th ed., Wiley,
[60] M. B. Smith, J. March in Advanced Organic Chemistry, Wiley, New York, 1992, pp. 446 – 447; b) I. Rachlin, H. Gurien, D. P.
New York, 5th ed., 2001, pp. 732 – 734. Wagner, Org. Synth. 1971, 51, 8 – 11.
[61] A. F. Shepard, N. R. Winslow, J. R. Johnson, J. Am. Chem. Soc.
[87] H. Wakamatsu, J. Furukawa, N. Yamakami, Bull. Chem. Soc.
1930, 52, 2083 – 2090.
Jpn. 1971, 44, 288.
[62] a) M. Nilsson, Acta Chem. Scan. 1966, 20, 423 – 426; b) M.
[88] K. Nagayama, F. Kawataka, M. Sakamoto, I. Shimizu, A.
Nilsson, C. Ullenius, Acta Chem. Scand. 1968, 22, 1998 – 2002.
Yamamoto, Chem. Lett. 1995, 367 – 368.
[63] A. Cairncross, J. R. Roland, R. M. Henderson, W. F. Shepard, J.
[89] a) K. Nagayama, I. Shimizu, A. Yamamoto, Chem. Lett. 1998,
Am. Chem. Soc. 1970, 92, 3187 – 3190.
1143 – 1144; b) K. Nagayama, I. Shimizu, A. Yamamoto, Bull.
[64] T. Cohen, R. A. Schambach, J. Am. Chem. Soc. 1970, 92, 3189 –
Chem. Soc. Jpn. 2001, 74, 1803 – 1815.
3190.
[90] L. J. Gooßen, K. Ghosh, Chem. Commun. 2002, 836 – 837.
[65] T. Cohen, R. W. Berninger, J. T. Wood, J. Org. Chem. 1978, 43,
[91] a) R. K. Dieter, Tetrahedron 1999, 55, 4177 – 4236; b) M. P. Sibi,
837 – 848.
Org. Prep. Proced. Int. 1993, 25, 15 – 40; c) V. Farina, V.
[66] a) R. A. Snow, C. R. Degenhardt, L. A. Paquette, Tetrahedron
Krishnamurthy, W. Scott, Org. React. 1997, 50, 1 – 652.
Lett. 1976, 17, 4447; b) U. Biermann, W. Friedt, S. Lang, W.
[92] S. Nahm, S. M. Weinreb, Tetrahedron Lett. 1981, 22, 3815 – 3818.
LShs, G. MachmSller, J. O. Metzger, M. RSsch gen. Klaas, H. J.
[93] R. C. Larock in Comprehensive Organic Transformations,
SchHfer, M. P. Schneider, Angew. Chem. 2000, 112, 2292 – 2310;
Angew. Chem. Int. Ed. 2000, 39, 2206 – 2224. VCH, New York, 1989, pp. 701 – 702.
[67] a) H. G. Rule, F. R. Smith, J. Chem. Soc. 1937, 1096 – 1103; [94] L. Liebeskind, J. Srogl, J. Am. Chem. Soc. 2000, 122, 11260 –
b) P. H. Leake, Chem. Rev. 1956, 56, 27 – 48; c) J. March, J. 11261.
Chem. Educ. 1963, 40, 212 – 213. [95] L. J. Gooßen, K. Ghosh, Angew. Chem. 2001, 113, 3566 – 3568;
[68] In contrast, malonic acids and phenylacetic acids can also be Angew. Chem. Int. Ed. 2001, 40, 3458 – 3460.
decarboxylated with catalytic amounts of Cu: a) O. Toussaint, [96] L. J. Gooßen, K. Ghosh, Eur. J. Org. Chem. 2002, 3254 – 3256.
P. Capdevielle, M. Maumy, Synthesis 1986, 1029 – 1031; b) O. [97] a) L. J. Gooßen, D. Koley, H. Hermann, W. Thiel, J. Am. Chem.
Toussaint, P. Capdevielle, M. Maumy, Tetrahedron 1984, 40, Soc. 2005, 127, 11 102 – 11 114; b) L. J. Gooßen, D. Koley, H.
3229 – 3233; c) O. Toussaint, P. Capdevielle, M. Maumy, Tetra- Hermann, W. Thiel, Organometallics 2006, 25, 54 – 67.
hedron Lett. 1987, 28, 539 – 542. [98] C. Amatore, A. Jutand, Acc. Chem. Res. 2000, 33, 314 – 321.
[69] R. Pfirmann, H. Schubert, Eur. Pat. Appl. EP741122, 1996. [99] R. Kakino, S. Yasumi, I. Shimizu, A. Yamamoto, Bull. Chem.
[70] L. J. Gooßen, W. R. Thiel, N. RodrWguez, C. Linder, B. Melzer, Soc. Jpn. 2002, 75, 137 – 148.
Adv. Synth. Catal. 2007, 349, 2241 – 2246. [100] a) R. Kakino, H. Narahashi, I. Shimizu, A. Yamamoto, Chem.
[71] J. S. Dickstein, C. A. Mulrooney, E. M. OXBrien, B. J. Morgan, Lett. 2001, 1242 – 1243; b) A. Yamamoto, Bull. Chem. Soc. Jpn.
M. C. Kozlowski, Org. Lett. 2007, 9, 2441 – 2444. 2002, 74, 1333 – 1345.
[72] L. J. Gooßen, G. Deng, L. M. Levy, Science 2006, 313, 662 – 664. [101] L. J. Gooßen, L. Winkel, A. DEhring, K. Ghosh, J. Paetzold,
[73] L. J. Gooßen, N. RodrWguez, B. Melzer, C. Linder, G. Deng, Synlett 2002, 1237 – 1240.
L. M. Levy, J. Am. Chem. Soc. 2007, 129, 4824 – 4833. [102] L. J. Gooßen, K. Ghosh, Chem. Commun. 2001, 2084 – 2085.
[74] J.-M. Becht, C. Catala, L. D. Cedric, C. Le Drian, A. Wagner, [103] H. Tatamidani, F. Kakiuchi, N. Chatani, Org. Lett. 2004, 6,
Org. Lett. 2007, 9, 1781 – 1783. 3597 – 3599.
[75] L. J. Gooßen, C. Linder, Saltigo GmbH, patent application [104] K.-C. Lim, Y.-T. Hong, S. Kim, Synlett 2006, 1851 – 1854.
filed, P10100016A, 2007. [105] R. Kakino, I. Shimizu, A. Yamamoto, Bull. Chem. Soc. Jpn.
[76] L. J. Gooßen, N. RodrWguez, C. Linder, unpublished results. 2001, 74, 371 – 376.
[77] L. J. Gooßen, B. Zimmermann, T. Knauber, Angew. Chem. [106] G. Frost, K. J. Wadsworth, Chem. Commun. 2001, 23 216 –
2008, DOI: 10.1002/ange.200800728; Angew. Chem. Int. Ed. 23 217.
2008, DOI: 10.1002/anie.200800728. [107] J. Tsuji, K. Ohno, Synthesis 1969, 157 – 169.
Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org 3119
Reviews L. J. Gooßen et al.
[108] J. A. Miller, J. A. Nelson, M. P. Byrne, J. Org. Chem. 1993, 58, [117] L. J. Gooßen, J. Paetzold, Angew. Chem. 2004, 116, 1115 – 1118;
18 – 20. Angew. Chem. Int. Ed. 2004, 43, 1095 – 1098.
[109] L. J. Gooßen, N. RodrWguez, Chem. Commun. 2004, 724 – 725. [118] a) A. M. CastaYo, A. M. Echavarren, Tetrahedron Lett. 1990,
[110] B. M. Trost, F. Chen, Tetrahedron Lett. 1971, 12, 2603 – 2607. 31, 4783 – 4786; b) A. M. CastaYo, A. M. Echavarren, Tetrahe-
[111] H. U. Blaser, A. Spencer, J. Organomet. Chem. 1982, 233, 267- dron Lett. 1993, 34, 4361 – 4362; c) A. M. CastaYo, A. M.
274. Echavarren, Organometallics 1994, 13, 2262 – 2268.
[112] T. Sugihara, T. Satoh, M. Miura, M. Nomura, Adv. Synth. Catal. [119] E. M. OXBrien, E. A. Bercot, T. Rovis, J. Am. Chem. Soc. 2003,
2004, 346, 1765 – 1772. 125, 10498 – 10499.
[113] T. Sugihara, T. Satoh, M. Miura, Tetrahedron Lett. 2005, 46, [120] L. J. Gooßen, J. Paetzold, Adv. Synth. Catal. 2004, 346, 1665 –
8269 – 8271. 1668.
[114] M. S. Stephan, A. J. J. M. Teunissen, G. K. M. Verzijl, J. G. [121] Note added in proof: A related procedure has very recently
de Vries, Angew. Chem. 1998, 110, 688 – 690; Angew. Chem. Int. been published in which copper is required only in catalytic
Ed. 1998, 37, 662 – 664. amounts: J. M. Villalobos, J. Srogl, L. S. Liebeskind, J. Am.
[115] L. J. Gooßen, J. Paetzold, L. Winkel, Synlett 2002, 1721 – 1723. Chem. Soc. 2007, 129, 15734 – 15735.
[116] L. J. Gooßen, J. Paetzold, Angew. Chem. 2002, 114, 1285 – 1289;
Angew. Chem. Int. Ed. 2002, 41, 1237 – 1241.
3120 www.angewandte.org 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2008, 47, 3100 – 3120