Nickel-Catalyzed C-O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains

Article abstract of DOI:10.1021/acscatal.7b00941

Two efficient protocols for the nickel-catalyzed aryl-alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C-O and aryl C-O bonds and allow the aryl-alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C-O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.

Full text of DOI:10.1021/acscatal.7b00941

Research Article
pubs.acs.org/acscatalysis
Nickel-Catalyzed C−O Bond-Cleaving Alkylation of Esters: Direct
Replacement of the Ester Moiety by Functionalized Alkyl Chains
Xiangqian Liu,† Jiaqi Jia,† and Magnus Rueping*,†,‡
†Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
‡KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi
Arabia
S
* Supporting Information
ABSTRACT: Two efficient protocols for the nickel-catalyzed aryl−alkyl cross-coupling reactions using esters as coupling
components have been established. The methods enable the selective oxidative addition of nickel to acyl C−O and aryl C−O
bonds and allow the aryl−alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C−O bond with high
efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of
widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.
KEYWORDS: cross-coupling, C−O activation, alkylation, decarbonylation, nickel catalysis
Scheme 1. Nickel-Catalyzed Decarbonylative C−C and C−O
Bond Cleavage Alkylation of Esters
INTRODUCTION
■
Transition-metal-catalyzed cross-coupling of organic halides
with organic and organometallic substrates has emerged as a
powerful method for the construction of carbon−carbon and
carbon−heteroatom bonds in modern chemical science.1
Moreover, the development of unconventional transformations
through cross-coupling reactions via activation of unreactive
bonds/groups led to the accomplishment of many valuable yet
challenging organic syntheses in recent years. Esters, as
fundamental synthetic materials, are generally employed as
protecting groups in synthetic chemistry owing to their
inertness to many reaction conditions. The development of
new methodologies, utilizing esters as coupling components,
will not only provide halogen-free synthetic processes but also
open access to the unconventional, streamlined functionaliza-
tion of a vast number of cheap and readily available esters and
their precursors, carboxylic acids and phenols. However, the
employment of esters as electrophiles in the cross-coupling
arena still poses formidable challenges. The main challenge is
the site-selectivity issue due to the presence of multiple C−O
reactive sites (Scheme 1). On one hand, the oxidative addition
of ester to the metal catalyst through acyl C−O bond cleavage
generates acyl−metal species, and the subsequent extrusion of
carbon monoxide forms metal−carbon monoxide complexes
and leads to decarbonylative couplings (Scheme 1, path a). On
the other hand, overcoming the high activation barrier for the
scission of an aryl C−O bond of esters produces aryl−metal
species directly and enables aryl C−O bond-cleaving reactions.
The oxidative addition of the metal catalyst to acyl C−O or to
aryl C−O bond leads to different reaction pathways. The ability
to control the site-selectivity of the oxidative addition and
selectively functionalize specific coupling components would
not only dramatically expand the utility of esters but also
broaden the synthetic repertoire.
In addition to the palladium−copper-catalyzed decarbox-
ylative biaryl coupling of aromatic carboxylic acids and
haloarenes,2a a number of decarboxylative/decarbonylative
cross-coupling reactions have been reported.2−8
Regarding the use of nickel for the decarbonylation of esters,
despite early reports by Yamamoto et al. on the stoichiometric
Ni(0)-mediated decarbonylation of aryl carboxylates via acyl
Received: March 23, 2017
Revised: May 11, 2017
© XXXX American Chemical Society
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Research Article
metal species in the late 1970s,9,10 nickel-catalyzed decarbon-
ylative C−C coupling reactions through the reaction of
phenolic esters with 1,3-azoles6a,b and arylboronic acids6c
have been reported only recently by Itami and Yamaguchi.
Despite the advances realized, a highly general protocol for the
decarbonylative aryl−alkyl cross-coupling reaction is still highly
demanded. Regarding the application of phenol derivatives in
the cross-coupling arena, a rather limited number of reactions
has been reported through the activation of aryl C−O bond of
ester derivatives.11,12 The nickel-catalyzed cross-coupling of
alkenyl/aryl pivalates with aryl zinc reagents has been reported
by Shi.11b Furthermore, iron-mediated alkenyl/aryl−alkyl cross-
coupling reactions of alkenyl/aryl carboxylates with Grignard
reagents have been reported by Shi and Jacobi von Wangelin.13
However, the use of Grignard reagents can sometimes be
limited with regard to functional group tolerance.
Therefore, the development of new protocols that enable the
selective alkylation of the two potential coupling components
of esters is highly desirable. Herein, we describe the first nickel-
catalyzed alkylation of esters in which a selective alkylation of
either the carboxylic acid component via decarbonylative bond
cleavage or the phenol component via cleavage of C−O bond14
occurs.
Table 1. Optimization of the Reaction Conditions (1a =
phenyl 2-naphthoate, 2a = 2-naphthyl pivalate)
a
yield (%)
entry
1a/2a
ligand (mol %)
temp (°C)
4a
4a′
1
2
3
4
5
1a
1a
1a
1a
1a
1a
1a
1a
1a
1a
2a
2a
2a
2a
2a
2a
iPr·HCl (20)
SiPr·HCl (20)
PCy3 (20)
150
150
150
150
150
150
150
150
150
150
70
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
17
5
PnBu3 (20)
dcype (10)
dcype (10)
dcype (10)
dcype (10)
dcype·2HBF4 (10)
dcype (5)
84
45
43
71
28
0
b
6
c
7
d
8
d
9
e
10
f
11
dcype (5)
99
73
83
93
87
0
f
12
dcype (5)
60
g
13
dcype (5)
70
h
14
dcype (5)
70
h
15
dcype·2HBF4 (5)
dcype (5)
70
RESULTS AND DISCUSSION
■
e
16
70
To achieve our goal in developing a successful decarbonylative
alkylation of esters, we began to search for viable catalytic
systems and nucleophiles, and our attention was drawn on
organozinc reagents as an alkyl source. Beside their
straightforward preparation, high reactivity/selectivity, and
high functional group tolerance, organozinc reagents proved
to be excellent transmetalation reagents in aryl−alkyl and
alkyl−alkyl cross-coupling reactions.15 Phenyl esters of aryl
carboxylic acids were selected as electrophiles, and the initial
investigation focused on the nickel-catalyzed decarbonylative
coupling of phenyl 2-naphthoate (1a) with n-pentylzinc
bromide (3a).
a
Reaction conditions: 1a/2a (0.25 mmol), 3a (0.5 mmol), Ni(cod)2
(0.025 mmol), THF/iPr2O (1.5 mL), sealed tube, 18 h, yield of the
b
c
d
isolated product. In THF (1.5 mL). THF/toluene (1.5 mL). NiCl2
(0.025 mmol) was used. Without Ni(cod)2. Ni(cod)2 (0.0125 mmol)
was used. 3a (0.275 mmol) was used. NiCl2 (0.0125 mmol) was
e
f
g
h
used.
effectively be applied. Control experiments showed that no
alkylation reaction proceeded in the absence of the nickel
catalyst (Table 1, entries 10 and 16).
Encouraged by our initial studies, we next examined a series
of phenyl esters of aryl carboxylic acids to determine the scope
of the new decarbonylative alkylation. As shown in Table 2, a
range of electronically and sterically diverse phenyl esters were
found to be cross-coupled with n-pentylzinc bromide in good
to excellent yields. Both naphthoic acid esters and simple
benzoic acid esters (1a−h) underwent the decarbonylative
coupling smoothly. Ketone groups, which are typically sensitive
to organometallic reagents, were also tolerated in the
transformation (1i, 1j). Although nickel catalysts facilitate the
functionalization of anisoles and amides, we found that, under
our conditions, the methoxy (1c, 1g) and amide (1k) groups
did not compete with the decarbonylative reaction. Further-
more, esters of heterocycles (1l−n) were also compatible with
the reaction conditions and yielded the products in moderate to
good yields.
Subsequently, we performed the decarbonylative cross-
coupling with various alkylzinc bromides 3 (Table 3). The
scope of this cross-coupling includes alkylzinc bromides ranging
from the short chain isobutylzinc bromide (3b) to those
bearing long alkyl chains (3c−f). Furthermore, alkylzinc
bromides with alkenyl (3d) and ether moieties (3e, 3f) as
well as a cyclopentyl derivative (3g) underwent the decarbon-
ylative alkylation reaction smoothly and produced the desired
products in good yields.
Ligands play a vital role in the activation of unreactive bonds,
and therefore, various ligands were evaluated in our trans-
formation. First, N-heterocyclic carbene (NHC) ligands were
examined; however, they did not promote the transformation
(Table 1, entries 1 and 2). Further screening showed that the
use of monodentate phosphine ligands PCy3 and P(nBu)3 gave
promising results (Table 1, entries 3 and 4). Gratifyingly, when
the bidentate phosphine ligand dcype was employed, the yield
of the decarbonylative product 4a increased to 84% (Table 1,
entry 5). The solvent plays also an important role in our
coupling reaction as replacement of iPr2O with THF or toluene
as cosolvent dramatically decreased the yield (Table 1, entries 6
and 7). The yield decreased if NiCl2 as catalyst and dcype·
2HBF4 as ligand were used (Table 1, entry 9). The robust
pivaloyl group proved to be less prone to undergo acyl C−O
bond scission in recent C−O bond activation reactions.
Interestingly, when we switched to 2-naphthly pivalate as
substrate, the aryl C−O bond cleavage coupling product 4a was
isolated in quantitative yield (99%) when the reaction was
performed with 5 mol % of Ni(cod)2 and 5 mol % of dcype at
70 °C (Table 1, entry 11). A lower temperature was found to
be detrimental to the yield (Table 1, entry 12). Decreasing the
amount of n-pentylzinc bromide led also to a slightly lower
yield (Table 1, entry 13). The use of NiCl2 as catalyst and
dcype·2HBF4 as ligand led to a lower yield (Table 1, entry 15).
However, this means that less sensitive Ni(II) salts can
Following the successful establishment of the decarbonylative
alkylation of phenyl esters, we turned our attention to examine
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Table 2. Substrate Scope of Phenyl Esters for the
Decarbonylative Alkylation (R = n-pentyl)
Table 3. Substrate Scope of Alkylzinc Bromides for the
Decarbonylative Alkylation
a
a
a
Reaction conditions: 1a (0.25 mmol), 3 (0.5 mmol), Ni(cod)2 (0.025
mmol, 10 mol %), dcype (0.025 mmol, 10 mol %), iPr2O/THF (1.5
mL), sealed reaction tube, 150 °C, 18 h.
At the same time, the scope and generality of alkylzinc
reagents were examined under our cross-coupling conditions
(Table 5). The scope of this C−O bond cleavage cross-
coupling includes alkylzinc reagents ranging from the short
ethylzinc bromide (3h) to those bearing long alkyl chains (3j−
o). The chemoselectivity profile of this reaction was nicely
illustrated by the fact that functional substituents such as iBu
(3b), phenyl (3i), alkenyl (3d, 3j), ether (3e), silyl ether (3k),
ester (3l, 3m), and amide (3n) moieties were tolerated under
our conditions. It is worth mentioning that the cross-coupling
reaction with 3o occurred efficiently, with the potential reactive
C−Cl bond untouched, yielding the chlorine-containing
product in 88%. Furthermore, the protocol could also be
applied to secondary alkylzinc bromides such as cyclopentyl,
cyclohexyl, and cyclopropyl derivatives (3g, 3p, 3q) and
proceeded smoothly with high efficiency. However, the use of
isopropylzinc bromide (3r) led to the linear product, most
probably due to an isomerization side reaction during the cross-
coupling process.16
The (+)-naproxen is a nonsteroidal anti-inflammatory drug
usually employed for the alleviation of pain, fever, and
inflammation.17 The modification of naproxen could produce
potential drug candidates.18 By employing our alkylation
methodology, we succeeded in synthesizing two naproxen
analogues, 8a and 8b, otherwise not easily accessible (Scheme
2). Starting from 2-naphthol, bromide 5 was readily prepared
according to a previous report.19 The active/directing ability of
phenols was illustrated by the bromination at C1 and C6 of 2-
naphthol. Due to the orthogonal reactivity of aryl bromides and
pivalates, a site-selective alkylation was performed to replace
the bromide with the propionate side chain.20 The alkylation
took place with high efficiency at the pivalate position when
pivalate 6 was employed in our nickel-catalyzed alkylation
process. Exposing dialkylated naphthalene 7 to acid conditions
overnight, the corresponding naproxen analogues 8a and 8b
were obtained in quantitative yields.
a
Reaction conditions: 1 (0.25 mmol), 3a (0.5 mmol), Ni(cod)2 (0.025
mmol, 10 mol %), dcype (0.025 mmol, 10 mol %), THF/iPr2O (1.5
mL), sealed reaction tube, 150 °C, 18 h. 3a (0.25 mmol) was used.
b
the reactivity and functional group tolerance of the C−O bond-
cleaving alkylation of pivaloyl esters (Table 4). A wide range of
pivaloyl esters 2b−s bearing electron-neutral, electron-donat-
ing, and electron-withdrawing substituents were smoothly
converted into the desired products. Phenyl derivatives 2i−o
with para-, meta-, and ortho-substitutions were evaluated and
underwent the reaction smoothly. Interestingly, substrates
bearing methoxy (2e, 2k, 2m), TMS (2f), amide (2h), and
dioxole (2l) groups were tolerated, providing the correspond-
ing products in good to excellent yields. Significantly, ester
groups were also tolerated under our conditions, showing their
orthogonal reactivity to pivaloyl groups (2g, 2n, 2o).
Heterocyclic derivatives 2p−s could also undergo the alkylation
process, providing alkyl heterocyclic products in good to
excellent yields.
CONCLUSIONS
■
In conclusion, we have developed two nickel-catalyzed aryl−
alkyl cross-coupling reactions using esters as electrophilic
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Table 4. Substrate Scope of Aryl Pivalates for the C−O Bond
Table 5. Substrate Scope of Alkylzinc Bromides for the C−O
a
a
Cleavage Alkylation
Bond Cleavage Alkylation
a
Reaction conditions: 2a (0.25 mmol), 3 (0.5 mmol), Ni(cod)2
(0.0125 mmol, 5 mol %), dcype (0.0125 mmol, 5 mol %), iPr2O/
b
THF (1.5 mL), sealed reaction tube, 70 °C, 18 h. 2-Propylnaph-
thalene was formed.
Scheme 2. Synthesis of Naproxen Analogues 8
a
Reaction conditions: 2 (0.25 mmol), 3a (0.5 mmol), Ni(cod)2
(0.0125 mmol, 5 mol %), dcype (0.0125 mmol, 5 mol %), iPr2O/
b
THF (1.5 mL), sealed reaction tube, 70 °C, 18 h. 3a (0.75 mmol)
c
was used. 3a (0.75 mmol), Ni(cod)2 (0.025 mmol), dcype (0.025
d
mmol), 130 °C, 72 h. 3a (1.0 mmol), Ni(cod)2 (0.05 mmol), dcype
e
(0.05 mmol), 130 °C, 72 h. Ni(cod)2 (0.025 mmol), dcype (0.025
f
mmol), 110 °C. Ni(cod)2 (0.025 mmol) and dcype (0.025 mmol)
were used.
coupling partners. The right choice of ester and catalyst allows
controlling the selective oxidative addition of nickel to an acyl
C−O or an aryl C−O bond, thus allowing the selective
introduction of alkyl groups to the carboxylic acid component
via decarbonylative bond cleavage or phenol component via
C−O bond cleavage. The protocols are characterized by their
efficiency and functional group tolerance with regard to both
coupling partners. The newly developed aryl−alkyl cross-
coupling reactions described herein may not only become a
good alternative to the standard halide-based cross-couplings
but also lead to late-stage synthetic strategies and unconven-
tional utilization of esters and their carboxylic acid and phenol
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.7b00941.
■
S
(7) Deamidative cross-couplings: (a) Meng, G.; Szostak, M. Angew.
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(e) Dey, A.; Sasmal, S.; Seth, K.; Lahiri, G. K.; Maiti, D. ACS Catal.
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Detailed experimental procedures, spectral data for all
1
compounds, and copies of H and 13C NMR spectra
(PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: magnus.rueping@rwth-aachen.de.
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Magnus Rueping: 0000-0003-4580-5227
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
X.L. was supported by the China Scholarship Council.
■
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