Nickel-Catalyzed Csp2-Csp3 Cross-Coupling via C-O Bond Activation

Article abstract of DOI:10.1021/acscatal.6b00801

A new and efficient nickel-catalyzed alkylation of C_Ar-O electrophiles with B-alkyl-9-BBNs is described. The transformation is characterized by its functional group tolerance and provides a practical and versatile access to various C_sp2

Full text of DOI:10.1021/acscatal.6b00801

Letter
pubs.acs.org/acscatalysis
Nickel-Catalyzed Csp2−Csp3 Cross-Coupling via C−O Bond Activation
Lin Guo,† Chien-Chi Hsiao,† Huifeng Yue,† Xiangqian Liu,† and Magnus Rueping*,†,‡
†Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
‡King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal 23955-6900, Saudi
Arabia
S
* Supporting Information
ABSTRACT: A new and efficient nickel-catalyzed alkylation
of CAr−O electrophiles with B-alkyl-9-BBNs is described. The
transformation is characterized by its functional group
tolerance and provides a practical and versatile access to
various Csp2−Csp3 bonds through Csp2−O substitution, without
the restriction of β-hydride elimination. Moreover, the
advantage of the newly developed method was demonstrated
in a selective and sequential C−O bond activation process.
KEYWORDS: nickel-catalyzed alkylation, B-alkyl-9-BBNs, C−O bond activation
n recent years, metal-catalyzed aromatic C−O bond
alkylboron compounds are widely employed in the total
synthesis of complex natural products and drug molecules, and
they play a key role in the synthesis of numerous functional
materials.9,10 Compared with alkyl zinc, alkyl magnesium, and
alkyl lithium reagents, the utilization of alkyl boron leads to
broad functional group tolerance under mild reaction
conditions and minimizes the β-hydride elimination proces-
s.5a,8c As the most widely used alkyl boron reagents, B-alkyl-9-
BBNs, which can be generated in situ from the corresponding
alkenes through hydroboration,11 have shown high efficiency
and tremendous potential in cross-coupling reactions with aryl
and alkenyl halides12 or triflates.13 Progress has been achieved
also in the field of Csp3−Csp3 cross-coupling with unactivated
alkyl electrophiles.14
Inspired by these studies, we set forth to develop a versatile
alkylation method that could overcome the limitations
associated with undesired side reactions. The potential of
coupling reactions of phenol derivatives would be enhanced
considerably if B-alkyl-9-BBNs could be employed as coupling
partners.
Herein, we describe a novel and versatile nickel-catalyzed
Csp2−Csp3 Suzuki-Miyaura cross-coupling reaction for the direct
alkylation of phenol derivatives via inert C−O bond activation,
while also enabling high reactivity and good substrate scope
(see Scheme 1).
We began our investigations by examining the reactivity of 2-
naphthyl pivalate (1a) with the B-alkyl-9-BBN 2a under nickel
catalysis (Table 1). First, we evaluated various nickel complexes
and found a promising result when employing Ni(IMes)2 and
cesium carbonate as base in diisopropyl ether (entries 1−4).
Further optimization gave a remarkable change in the reactivity
I
activation and functionalization has attracted considerable
attention in organic synthesis, particularly because of the lack of
toxicity, as well as ready availability and natural abundance of
phenols, compared with commonly used organic halides.1 In
this research field, nickel, because of its advantages in oxidative
addition as well as relatively low price,2 has emerged as a
powerful synthetic tool in carbon−carbon and carbon−
heteroatom bond-forming reactions3,4 with C−O electrophiles.
Unlike the comparatively facile Csp2−Csp2 cross-couplings,
only limited knowledge of nickel-catalyzed Csp2−Csp3 cross-
couplings has been gained if phenol derivatives are employed as
C−O electrophiles.5 The initial attempt was made in 2008 by
Shi and co-workers, who reported a one-step methylation
procedure through the use of methylmagnesium bromide.3d
Subsequently, our group reported an efficient dealkoxylative
alkylation of aryl ethers and enol ethers by employing a lithium
bifunctional nucleophile.6 The thereby-obtained α-carbon
active products are suitable for various further modifications;
however, additional steps are required. Furthermore, Chatani
and our group described the Csp2−Csp3 alkylation reaction of
anisole derivatives with alkyl Grignard and trialkyl aluminum
reagents.7 However, in a more general view, these protocols
have limitations regarding the scope of the alkyl groups
introduced. In this context, the discovery of new and versatile
protocols for Csp2−Csp3 cross-couplings that might lead to new
synthetic routes toward complex molecules synthesis attracted
our interest. In particular, the functional group tolerance was
not achieved so far and functional groups including esters,
alcohols, ethers, or N-containing substrates could not be
applied.
With these considerations in mind, we selected alkylboron
reagents as nucleophilic coupling partners, since Suzuki−
Miyaura cross-couplings have already emerged as one of the
most powerful tools in organic synthesis.8 Because of their
operational simplicity and environmentally benign nature,
Received: March 18, 2016
Revised: May 11, 2016
© XXXX American Chemical Society
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Letter
Control experiments revealed that the reaction could not be
initiated in the absence of the nickel catalyst (entry 17).
Under the optimal reaction conditions, various phenol
derivatives were further investigated. Tosylates (Table 2,
Scheme 1. Csp2−Csp3 Cross-Coupling of Phenol Derivatives
with B-Alkyl-9-BBNs
a
Table 2. Alkylation of Different Phenol Derivatives
a
Table 1. Optimization of the Cross-Coupling Reaction
b
entry
R
yield (%)
1
2
3
4
5
6
Ts
98
98
92
75
93
0
SO2NEt2
CONEt2
Boc
Piv
b
entry
Ni cat.
NiBr2
ligand
base
yield (%)
Me
a
1
2
IPr·HCl
IPr·HCl
IPr·HCl
none
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
tBuOK
CsF
0
0
Reaction conditions: 1 (0.20 mmol), 2a (0.32 mmol), Ni(COD)2 (8
mol %), IPr·HCl (16 mol %), Cs2CO3 (1.5 equiv), Pr2O (0.1 M) at
110 °C for 12 h. PMP = para-methoxyphenyl. Yield for isolated
products.
i
NiCl2·glyme
Ni(acac)2
b
3
11
21
90
10
26
0
4
Ni(IMes)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
none
5
IPr·HCl
SIPr·HCl
IMes·HCl
PCy3
6
entry 1) and sulfamates (entry 2) were efficient in the Csp2−
Csp3 coupling reaction, because of their comparatively high
reactivity toward C−O bond cleavage. Carbamates (entry 3)
and carbonates (entry 4), similar to pivalates 1a, also provided
smooth alkylation products. However, aryl methyl ethers (entry
6) as electrophiles were not feasible under the present reaction
conditions.
7
8
9
dppf
11
19
27
38
53
0
10
c
dcype
11
12
13
14
15
16
17
IPr·HCl
IPr·HCl
IPr·HCl
IPr·HCl
IPr·HCl
IPr·HCl
IPr·HCl
K3PO4
Encouraged by our initial results, we next examined a series
of electrophiles containing inert C−O bonds to determine the
scope of the cross-coupling reaction. As shown in Table 3, a
wide range of pivalate substrates could be transformed to the
desired products efficiently by employing B-alkyl-9-BBN 2a as a
coupling partner. Naphthyl (1a, 1b), phenanthryl (1c), and
biphenyl (1d−1f) pivalates were suitable for the transformation
and showed high reactivity. Derivatives of naphthyl pivalates
bearing a methoxy group at the 4- or 7-position gave the
corresponding coupling products in good yields (3g, 3h).
Notably, the chemoselectivity profile of this method was nicely
illustrated in that functional groups such as ketone (3k),
fluoride (3l), ester (3i), and TMS moieties (3j) were perfectly
tolerated under the present conditions. It was further
demonstrated that the nitrogen-containing heterocycles (1m)
did not interfere with the productive alkylation. Furthermore,
good to moderate yields were obtained for the alkylation of
dihydronaphthyl pivalates (1n, 1o) and diphenylvinyl pivalate
(1p), which indicates that this methodology can be applied also
to alkenyl pivalates. In a scale-up experiment with only 2 mol %
of catalyst and 4 mol % of ligand, 1.0 g of 2-naphthyl pivalate
(1a) was transformed into the corresponding product 3a in
46% yield.
Next, we turned our attention to study the preparative scope
of various B-alkyl-9-BBN nucleophiles by utilizing 2-naphthyl
pivalate 1a as a coupling electrophile. As shown in Table 4, a
wide array of functional groups from the alkylborane reagents
were compatible with the cross-coupling conditions, including
methyl (4b), methoxy (4c), fluoride (4d), trifluoromethyl (4e),
benzodioxole (4f), indole (4h), and ether (4i). Furthermore,
aliphatic rests (4k, 4l) are also perfectly suitable for the cross-
coupling protocol, which could further enhance the utility and
compatibility of this method.
none
d
e
Cs2CO3
Cs2CO3
Cs2CO3
97 (93)
df
,
91
0
a
PMP
=
para-methoxyphenyl. IPr·HCl
=
1,3-bis(2,6-
diisopropylphenyl)imidazolium chloride. SIPr·HCl = 1,3-bis(2,6-
diisopropylphenyl)imidazolinium chloride. IMes·HCl = 1,3-bis(2,4,6-
trimethylphenyl)imidazolinium chloride. dppf = 1,1′-ferrocenediyl-
bis(diphenylphosphine). dcype = 1,2-bis(dicyclohexylphosphino)-
ethane. Reaction conditions: 1a (0.20 mmol), 2a (0.32 mmol), Ni
catalyst (8 mol %), ligand (16 mol %), base (1.5 equiv), iPr2O (0.1 M)
b
at 100 °C for 12 h. NMR yields using 1,3,5-(OMe)3C6H3 as an
c
d
e
internal standard. iBuOH (2.0 equiv) was added. 110 °C. Yield for
f
isolated compound. Ni catalyst (5 mol %), ligand (10 mol %).
and the desired product 3a was isolated in 90% NMR yield
when Ni(COD)2/IPr·HCl catalytic system was applied (entry
5). Other carbene and phosphine ligands were also investigated
in order to identify the best ligand candidate for this coupling
reaction. As shown in entries 6−10, the use of other N-
heterocyclic carbenes (entries 6 and 7) or phosphine ligands
(entries 8−10) could not improve the yield further and
invariably resulted in hydrolyzed 2-naphthol or reduced
naphthalene as byproducts. In addition, the choice of base
was also crucial for the success of this Suzuki−Miyaura coupling
reaction, because of its effect on the hydrolysis of the pivalate
group.12a,15
The yield was much lower when tBuOK, CsF, or K3PO4 were
used (entries 11−13) and no product was obtained in the
absence of base (entry 14). Furthermore, a slight increase in
temperature (entry 15) furnished 3a in 97% NMR yield and
93% isolated yield, whereas the yield slightly decreased if 5
mol % Ni(COD)2 and 10 mol % IPr·HCl were used (entry 16).
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Letter
ab
,
a b
,
Table 3. Scope for the Phenol Derivatives
Table 4. Scope for the Alkylboranes
a
Reaction conditions: 1a (0.20 mmol), 2 (0.32 mmol), Ni(COD)2 (8
i
mol %), IPr·HCl (16 mol %), Cs2CO3 (1.5 equiv), Pr2O (0.1 M) at
110 °C for 12 h. Isolated yields. Reaction time: 24 h.
b
c
Scheme 2. Programmed Selective C−O Bond Activation
a
Reaction conditions: 1 (0.20 mmol), 2a (0.32 mmol), Ni(COD)2 (8
mol %), IPr·HCl (16 mol %), Cs2CO3 (1.5 equiv) in iPr2O (0.1 M) at
b
c
110 °C for 12 h. Isolated yields. Reaction conditions: 1 (4.38 mmol),
2a (7.01 mmol), Ni(COD)2 (2 mol %), IPr·HCl (4 mol %), Cs2CO3
d
(1.5 equiv) in iPr2O (0.2 M) at 110 °C for 68 h. Reaction time: 24 h.
e
The reaction was performed at 120 °C for 48 h. 2a: Ralkyl
=
CH2CH2CH2PMP.
To demonstrate the advantage of our methodology, an
interesting application of selective and sequential C−O bond
activation was performed (Scheme 2). The difference in
reactivity among aryl tosylates, aryl pivalates, and aryl methyl
ethers provides a new possibility for the sequential function-
alization and elaboration of aromatic rings. Based on our
rational design, we synthesized the phloroglucinol derivative 5,
which contains three types of C−O bonds with different
reactivity.16 The less-inert C−OTs bond could be first activated
for arylation by palladium-catalyzed Suzuki−Miyaura cross-
coupling to achieve biphenyl 6. Applying our present method
to replace the pivalate group of 6 resulted in the alkylation
product 7. Subsequently, the highly inert C−OMe bond was
converted to 8 by using a method developed previously in our
research group, which provides the opportunity for further
modifications and transformations because of the functional
TMS moiety.
and industrial settings, the results provide new application
opportunities as the reactions avoid the use of halides and
sulfonates and allow displacement of the pivalate group, which
can be used as a directing group in C−H functionalization prior
to the dealkoxygenative alkylations.3j,17 This new protocol also
exhibits good compatibility with a variety of synthetically
important functional groups of phenol pivalates, as well as
alkylboranes. To further demonstrate the utility of this method,
a new strategy for sequential functionalization of aromatic rings
was performed by selective and sequential C−O bond
In summary, we have developed a new and practical way to
construct Csp2−Csp3 bonds by using B-alkyl-9-BBNs as a
coupling partner in nickel-catalyzed C−O bond activation.
Given the widespread utility of catalytic alkylations in academic
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transformations are currently underway in our laboratories.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.6b00801.
■
S
Detailed experimental procedures, spectral data for all
compounds, and copies of 1H, 13C, and 19F NMR spectra
(PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail: magnus.rueping@rwth-aachen.de.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
L.G., H.Y., and X.L. gratefully acknowledge the China
Scholarship Council. C.-C.H. gratefully acknowledges DAAD
for fellowship.
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Tetrahedron 1997, 53, 539. (b) Zheng, W.; DeMattei, J. A.; Wu, J.-
P.; Duan, J. J. W.; Cook, L. R.; Oinuma, H.; Kishi, Y. J. Am. Chem. Soc.
1996, 118, 7946.
(14) For selected Csp3−Csp3 Suzuki−Miyaura couplings, see:
(a) Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992,
691. (b) Netherton, M. R.; Dai, C.; Neuschuetz, K.; Fu, G. C. J. Am.
Chem. Soc. 2001, 123, 10099. (c) Kirchhoff, J. H.; Dai, C.; Fu, G. C.
Angew. Chem., Int. Ed. 2002, 41, 1945. (d) Brenstrum, T.; Gerristma,
D. A.; Adjabeng, G. M.; Frampton, C. S.; Britten, J.; Robertson, A. J.;
McNulty, J.; Capretta, A. J. Org. Chem. 2004, 69, 7635. (e) Arentsen,
K.; Caddick, S.; Cloke, F. G. N.; Herring, A. P.; Hitchcock, P. B.
Tetrahedron Lett. 2004, 45, 3511. (f) Valente, C.; Baglione, S.; Candito,
D.; O’Brien, C. J.; Organ, M. G. Chem. Commun. 2008, 735.
(g) Achonduh, G. T.; Hadei, N.; Valente, C.; Avola, S.; O’Brien, C. J.;
Organ, M. G. Chem. Commun. 2010, 46, 4109. (h) Lu, Z.; Fu, G. C.
Angew. Chem., Int. Ed. 2010, 49, 6676.
(15) Sato, M.; Miyaura, N.; Suzuki, A. Chem. Lett. 1989, 1405.
(16) Zhao, F.; Zhang, Y.-F.; Wen, J.; Yu, D.-G.; Wei, J.-B.; Xi, Z.-F.;
Shi, Z.-J. Org. Lett. 2013, 15, 3230.
(17) Xiao, B.; Fu, Y.; Xu, J.; Gong, T.-J.; Dai, J.-J.; Yi, J.; Liu, L. J. Am.
Chem. Soc. 2010, 132, 468.
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DOI: 10.1021/acscatal.6b00801
ACS Catal. 2016, 6, 4438−4442