Markovnikov-Selective Palladium Catalyst for Carbonylation of Alkynes with Heteroarenes

Article abstract of DOI:10.1002/anie.201706794

A new class of palladium catalysts, based on heterocyclic diphosphines, was rationally designed and synthesized. Application of one of these catalysts allows novel Markovnikov-selective carbonylation of non-activated alkynes with heteroarenes to give the

Full text of DOI:10.1002/anie.201706794

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Accepted Article
Title: Markovnikov-selective Palladium Catalyst for Carbonylation of
Alkynes with Heteroarenes
Authors: Jie Liu, Haoquan Li, Ricarda Dühren, Jiawang Liu, Anke
Spannenberg, Robert Franke, Ralf Jackstell, and Matthias
Beller
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10.1002/anie.201706794
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Markovnikov-selective Palladium Catalyst for Carbonylation of
Alkynes with Heteroarenes
Jie Liu, Haoquan Li, Ricarda Dühren, Jiawang Liu, Anke Spannenberg, Robert Franke, Ralf Jackstell,
and Matthias Beller*
Dedication to Professor Dr. Lutz-Friedjan Tietze on the occasion of his 75th birthday.
Abstract: A new class of palladium catalysts based on heterocyclic
diphosphines are rationally designed and synthesized. Application of
one of these catalysts allows for novel Markovnikov-selective
carbonylation of non-activated alkynes with heteroarenes to give the
corresponding branched α,β-unsaturated ketones in excellent yields
(up to 97%) and regioselectivities (b:l up to 99:1). In addition to
heteroarenes, other common nucloephiles (alcohol, phenol, amine
and amide) furnish the desired carbonylation products smoothly in
high yields.
via this technology.[7] Since the original work of Reppe in the
past century,[8] carbonylation of alkynes with various
nucleophiles such as H2O,[9] alcohols (O-nucleophiles),[10] thiols
(S-nucleophiles)[11] and amines (N-nucleophiles)[12] have been
extensively studied and numerous catalysts are available for
producing all kinds of carbonyl compounds. On the other hand,
The development of ligands plays a key role in enabling new
transformations and fine-tuning the chemo- or regioselectivity in
homogenous
polymerizations, cross-coupling reactions, carbonylations,
hydrogenations and metathesis.[1] Although
plethora of
catalysis.
Illustrative
examples
include
a
nitrogen- and phosphorous-based ligands have been developed
over the last decades, their rational design to afford highly active
catalyst systems, which can be easily prepared and modified,
continues to be an important topic in this area.[2]
Among the privileged ligand classes known, especially bi-
and multidentate derivatives create highly stable and selective
organometallic complexes.[3] In these cases, properties and
performance can be varied by changing either the ligand
backbone or the substituents on the donor (e.g. phosphorus or
nitrogen) atoms through steric and electronic effects (Scheme
1a).[4] Inspired by the valuable DPEphos ligand[5] and pyrrole-
Scheme 1. a) Ligand modification and b) design of DPMPhos ligands.
based monophosphines (cataCxium®
P series) in various
carbonylative transformations and cross-coupling reactions,[6] we
had the idea to design diphosphine ligands containing N,N’-
dipyrrolylmethane backbone (Scheme 1b). Advantageously, we
expected these novel ligands to be conveniently prepared in
two-steps. Variation of the heterocycle and the phosphine
building blocks should generate related derivatives in a highly
modular manner.
the use of C-nucleophiles which creates synthetic important
ketones has been investigated to a lesser extent. In fact, only
one example utilizing indoles as C-nucleophiles in alkyne
carbonylation reactions has been reported by Alper and co-
workers and this methodology is limited to activated alkynes.[13]
To the best of our knowledge, Markovinkov selective
carbonylations of alkynes with heteroarenes are unknown, even
though the potential products that would arise from such
reactions have broad utility in organic synthesis. In this respect,
we report herein our recent investigations on the development of
a general and efficient palladium catalyst for the Markovinkov-
selective carbonylation of unactivated alkynes.
Carbonylation reactions belong to the most important
industrial applications in the area of homogeneous catalysis and
a variety of value-added bulk and fine chemicals are available
[*]
Dr. J. Liu, Dr. H. Li, R. Dühren, Dr. J. Liu, Dr. A. Spannenberg, Dr.
R. Jackstell, Prof. Dr. M. Beller
Some years ago, we reported the synthesis of 1-arylpyrrolyl-
and
–indolyl-2-phosphines,
which
have
been
also
Leibniz-Institut für Katalyse e.V. an der Universität Rostock
Albert-Einstein-Straße 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
commercialized (cataCxium® P series).[6a] Notably, these ligands
can be easily prepared by deprotonation at the α-position of the
heterocycle, thus allowing an efficient modular synthesis of all
kinds of related derivatives. In order to take advantage of this
activation for the generation of bidentate ligands, we had the
idea to use N,N’-dipyrrolylmethanes as a new scaffold. Indeed,
without pre-halogenation of N,N’-dipyrrolylmethanes, ligands L1
and L2 can be smoothly synthesized via directly lithiation with
Prof. Dr. R. Franke
Evonik Performance Materials GmbH
Paul-Baumann-Str. 1, 45772 Marl (Germany)
and
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum,
44780 Bochum (Germany)
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201706794
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two equivalent of nBuLi and subsequent coupling with
chlorodiphenylphosphine and chlorodicyclohexylphosphine,
respectively (Scheme 2a). A palladium complex was obtained by
treating L1 with Pd(MeCN)2Cl2 in 1,2-dichloroethane. The
structure of Pd(L1)Cl2 was confirmed by X-ray crystallography
(Scheme 2b).[14]
100
80
60
40
20
0
branched linear
Figure 1. Ligand effect for Markovnikov-selective carbonylation of 1a with 2a.
Reaction conditions: 1a (1.0 mmol), 2a (0.5 mmol), Pd(acac)2 (1.0 mol%),
bidentate ligand (2.0 mol%) or monodentate ligand (4.0 mol%), p-TsOH (5.0
mol%), CO (40 bar), toluene (1.0 mL), 70 °C, 12 h. Yields (3a and 3a’) and
regioselectivities were determined by GC analysis using isooctane as the
internal standard.
Scheme 2. a) Preparation of bis(2-(diphenylphosphanyl)-1H-pyrrol-1-
yl)methane; b) molecular structure of Pd(L1)Cl2 in the crystal. Displacement
ellipsoids correspond to 30% probability. Hydrogen atoms and co-crystallized
solvent are omitted for clarity.
With the new phosphine ligands in hand, the carbonylation of
1-octyne 1a with N-methylpyrrole 2a was investigated. We
observed a high yield (88%) and good selectivity (b/l = 91:9) for
the desired α,β-unsaturated ketone 3a in the presence of L1
(bis(2-(diphenylphosphanyl)-1H-pyrrol-1-yl)methane). However,
L2 bearing the electron-rich dicyclohexylphosphino groups,
suppressed this reaction. Similarly, using the imidazolyl-based
ligand L3, no desired product was obtained. Among the known
diphosphines with aryl-(hetero)aryl backbones L4-L6, L4 and
rac-binap L6 showed moderate reactivity. In contrast, applying
DPEphos L7 and dppf L8 led to high yields of 3a (81% and 80%,
respectively), while the more rigid ligand Xantphos L9 gave
much worse result. Other bidentate phosphine L10 and common
monodentate ligands such as PPh3 L11, PPh2Py L12,
cataCxium® P series L13 and L14 all exhibited no activity for this
carbonylation process. As expected, compared to the in situ
system using the defined Pd(L1)Cl2 complex led to the desired
product in comparable yield (86%) and good regioselectivity (b/l
= 90:10).
3-phenyl-1-propyne 1b and cyclohexylacetylene 1c were
converted smoothly to corresponding branched α,β-unsaturated
ketone 3b and 3c in good yields and regioselectivities.
Increasing the steric bulk of the terminal alkyne still led to good
branched selectivity of product 3d in moderate yield (70% yield,
87% b-selectivity). Aromatic alkynes like phenylacetylene
reacted smoothly and furnished an excellent yield and b-
selectivity of the desired product 3e (88% yield and 99% b-
selectivity). Alkynes containing halogen and nitrile group were
also efficiently converted into the desired products 3f and 3g
with good regioselectivities. Notably, when a conjugated enyne
was used, the double bond remained intact and only the triple
bond was selectively carbonylated to the branched ketone 3h in
81% yield with 99% b-selectivity. In addition to terminal alkynes,
different internal alkynes were investigated in this transformation
as well. The symmetrical alkyl and aryl alkynes underwent
efficient carbonylation to afford the corresponding α,β-
unsaturated ketones 3i and 3j with high stereoselectivity. The
After optimizing the reaction conditions (see Supporting
Information, Tables S1), we explored the general applicability of
our novel catalyst and the substrate scope. Here, at first
reactions of various alkynes 1 with N-methylpyrrole 2a were
studied (Scheme 3). In addition to 1a, aliphatic alkynes such as
carbonylation
of
an
unsymmetrical
alkyne,
methyl
phenylpropiolate, gave the product 3k in 56% yield with 99% E-
selectivity. Remarkably, 1,7-octadiyne also reacted smoothly
and gave the dicarbonylation product 3l in moderate yield. To
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note, all the C-H carbonylation reactions preferentially occurred
at C2 position on the pyrrole.
Additionally,
phenol
also
furnished
the
desired
alkoxycarbonylation product 3y in excellent yield and branched
selectivity. As an example of amine as nucleophile, N-
methylaniline worked well and the desired product 3z was
afforded in high isolated yield and selectivity. Last but not least,
a less nucleophilic substrate, such as caprolactam also reacted
smoothly to give the synthetically interesting imide 3aa in 99%
yield and b-selectivity.
Scheme 3. Markovnikov-selective carbonylation with different alkynes.
Reaction conditions: alkyne 1 (1.0 mmol), N-methylpyrrole 2a (0.5 mmol),
Pd(acac)2 (1.0 mol%), L1 (2.0 mol%), p-TsOH (5.0 mol%), CO (40 bar),
toluene (1.0 mL), 70 °C, 12 h. In each case, the yield of isolated compound 3
is given, and the number in the parenthesis indicates the 3/3’ ratio determined
by GC analysis. [a] Reaction at 90 °C. [b] Reaction at 100 °C for 20 h. E/Z
ratio is determined by GC analysis. [c] Reaction at 90 °C for 20 h. E/Z ratio is
determined by GC analysis.
Next, we employed structurally diverse heteroarenes as
nucleophiles (Scheme 4). For example, benzyl (Bn) protected
pyrrole also gave a branched selective carbonylation product 3m
in excellent yield.[15] Due to the importance of substituted indoles
it is exciting that N-methylindole is a suitable substrate to afford
the C3-carbonylated ketone in high yield and regioselectivity (3n,
96% yield, 98% b-selectivity). Exploring various indole
derivatives, we found that substituents including –Me (3o and
3p), –OMe (3q), –Br (3r), –Cl (3s) and –F (3t) at different
positions on the indole nucleus are all compatible with this
catalyst system. The desired Markovnikov products were
obtained exclusively at C3 position in 85%–97% yields.
Moreover, pyridine-containing scaffold 2u also worked well
under similar conditions to give the corresponding carbonylative
product 3u in moderate yield (67% yield). Interestingly, even
azulene led to a good yield of 71 % for 3v owing to its high
nucleophilicity.
Scheme 4. Markovnikov-selective carbonylation with various nucleophiles:
heteroarene, alcohol, phenol, amine and amide. Reaction conditions:
phenylacetylene 1e (1.0 mmol), nucleophile 2 (0.5 mmol), Pd(acac)2 (1.0
mol%), L1 (2.0 mol%), p-TsOH (5.0 mol%), CO (40 bar), toluene (1.0 mL),
70 °C, 12 h. In each case, the yield of isolated compound 3 is given, and the
number in the parenthesis indicates the 3/3’ ratio determined by GC analysis.
[a] Reaction at 90 °C. [b] Reaction at 100 °C.
Finally, we were interested in demonstrating the usefulness
of our products as intermediates in organic synthesis. Starting
from commercially available alkynes and heteroarenes, the
substituted cyclopentanones (4a to 4f) can be readily accessed
in a “one-pot” process when our carbonylation reaction is
combined with Nazarov cyclization[16] (Scheme 5). To the best of
our knowledge, this step-economical annulation process allows
for the most effective generation of such polycyclic ring products.
To demonstrate the generality for this catalyst, alkoxy- and
aminocarbonylations with diverse O- and N-containing
nucleophiles were investigated. For example, carbonylation of
phenylacetylene with 1-butanol and benzyl alcohol led to the
corresponding branched esters 3w and 3x efficiently.
In addition, the α,β-unsaturated ketone can be further
converted to γ-keto ester 5 in high yield via palladium catalyzed
alkoxycarbonylation (Scheme 6).[3f] Notably, 5 is an analogue of
Levulinic ester, which can be similarly used for further
valorization.[17]
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Keywords: diphosphine • carbonylation • Markovnikov-selective
• alkyne • ketone
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Scheme 6. Synthetisis of γ-keto ester.
In summary, we developed the first palladium catalyst
system for a Markovnikov-selective carbonylation of alkynes with
heteroarenes. By applying the novel ligand L1 (bis(2-
(diphenylphosphanyl)-1H-pyrrol-1-yl)methane), a wide range of
unactivated alkynes and heteroarenes as well as other
nucleophiles, such as alcohol, phenol, amine and amide, are
efficiently transformed into the corresponding branched α,β-
unsaturated products in good yields and often with high
regioselectivity. The general applicability of this methodology is
demonstrated by “one-pot” synthesis of polycyclic ring products.
In view of the easy availability of the substrates, the efficiency,
and the good regioselectivity, this novel catalyst system is
expected to complement the current methods for carbonylations
in homogenous catalysis and organic synthesis.
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Acknowledgements
We are grateful for the financial support from Evonik Industries
AG. J.L. thanks the Chinese Scholarship Council for financial
support. We also thank the analytical department in Leibniz-
Institute for Catalysis at the University of Rostock (LIKAT) for
their excellent technical and analytical support.
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Entry for the Table of Contents
COMMUNICATION
Jie Liu, Haoquan Li, Ricarda Dühren,
Jiawang Liu, Anke Spannenberg, Robert
Franke, Ralf Jackstell, and Matthias
Beller*
Page No. – Page No.
Markovnikov-selective Palladium
Catalyst for Carbonylation of Alkynes
with Heteroarenes
It’s a new cat: The ligand L1 (bis(2-(diphenylphosphanyl)-1H-pyrrol-1-yl)methane)
allows for a general palladium-catalyzed carbonylation of unactivated alkynes with
heteroarenes. The reaction proceeds smoothly to give the corresponding branched
α,β-unsaturated ketones in good yields (up to 97%) and often with high
Markovnikov-selectivity (b:l up to 99:1).
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