The Discovery of a Palladium(II)-Initiated Borono-Catellani Reaction

Article abstract of DOI:10.1002/anie.201803865

Reported is a novel palladium(II)-initiated Catellani-type reaction that utilizes widely accessible aryl boronic acids as the substrates instead of aryl halides, thereby greatly expanding the existing scope of this powerful transformation. This borono-Catellani reaction was promoted by cooperative catalysis between Pd(OAc)₂ and the inexpensive 5-norbornene-2-carbonitrile. Practicality is the striking feature of the reaction: it is run open to air at ambient temperature and no phosphine ligand is needed. This mild, chemoselective, and scalable protocol is compatible with a large range of readily available functionalized aryl boronic acids and bromides, as well as terminating olefins (50 examples, 39–97 % yields). Moreover, the orthogonal reactivity between the borono-Catellani and classical Catellani reaction was demonstrated. This work is expected to open new avenues for developing novel Catellani-type reactions.

Full text of DOI:10.1002/anie.201803865

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Accepted Article
Title: The Discovery of A Pd(II)-Initiated Borono-Catellani Reaction
Authors: Qianghui Zhou, Shuqing Chen, Ze-Shui Liu, Tao Yang, Yu
Hua, Zhiyu Zhou, and Hong-Gang Cheng
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The Discovery of A Pd(II)-Initiated Borono-Catellani Reaction
†
†
Shuqing Chen , Ze-Shui Liu , Tao Yang, Yu Hua, Zhiyu Zhou, Hong-Gang Cheng and Qianghui Zhou*
Dedicated to Prof. Xiyan Lu on the occasion of his 90th birthday
Abstract: We report a novel Pd(II)-initiated Catellani-type
reaction that utilizes widely accessible aryl boronic acids as the
substrates instead of aryl halides, thereby greatly expanding the
existing paradigm of this powerful transformation. This tentatively
called “Borono-Catellani reaction” was
promoted by a
cooperative catalysis of Pd(OAc) and the inexpensive 5-
2
norbornene-2-carbonitrile. Practicality is the striking feature of the
reaction: it is run at ambient temperature under air while no
phosphine ligand is needed. This mild, chemo-selective, and
scalable protocol is compatible with a large range of readily
available functionalized aryl boronic acids, bromides as well as
terminating olefins (50 examples, 39-97% yields). Moreover, the
orthogonal reactivity between the Borono-Catellani and classical
Catellani reaction was demonstrated. This work is expected to
open up new avenues for developing novel Catellani-type
reactions.
One of the central tasks in modern organic synthesis is to
develop efficient strategies for C-C bond construction. The
sequential activation of C-H bond and construction of C-C bond is
an appealing but particularly challenging pathway.[1] Nevertheless,
the Catellani reaction is one of the most promising approaches to
accomplish these processes.[2-3] It utilizes cooperative palladium
and norbornene catalysis to facilitate sequential ortho C–H
functionalization and ipso coupling of aryl iodide, thereby allowing
the simultaneous functionalization of both ortho and ipso positions
to permit the expeditious syntheses of highly substituted arenes
with high efficiencies and selectivities.[4] During the twenty years
of development, the substrates utilized for the Catellani-type
reactions are mainly limited to aryl halides,[3] and a Pd(0) initiated
cooperative catalysis mechanism was suggested.[4] Recently, the
Bach group revealed a novel Catellani-type reaction applying
substituted 1-H-indole and 1-H-pyrrole as the substrates, which
was believed to be promoted by Pd(II)-initiated cooperative
catalysis.[5] Later, the Yu group[6] and others[7] developed a meta-
C-H functionalization strategy of substituted arenes via a directed
Figure 1. Pd(0)- and Pd(II)-catalyzed Catellani reactions
applied as cross coupling partners,[9] catalysts[10] and so on. In
classical Catellani-type reactions, aryl boronic acids and their
derivatives mainly act as terminating reagents.[11] Nevertheless,
the innovative research from the Bach and Yu groups inspired us
to pursue a tentatively called "Borono-Catellani reaction" as
illustrated in Figure 1B, applying these readily available reagents
as the substrates. Prior to the start of this project, applying them
as the substrates instead of aryl iodides in Pd/NBE cooperative
catalysis had not been reported. Until very recently, Zhang and
co-workers reported a similar reaction.[12] As shown in Figure 1C,
we envisioned that the reaction would be initiated by a Pd(II)
catalyst, which reacts with aryl boronic acid 1 to afford arylPd(II)
intermediate I via transmetallation. The migratory insertion of
norbornene and subsequent ortho-C–H activation in the presence
of a base to form the key aryl/norbornene palladacycle complex
(ANP) III. The oxidative addition of alkyl halide 2 to III gives
palladium(IV) complex IV, which then undergoes reductive
elimination and subsequent extrusion of norbornene to afford
Pd(II) species VI. VI can be captured by the olefin 3 to provide the
Catellani product 4 and release a Pd(0) species, which is then
oxidized to regenerate the Pd(II) catalyst. Although the above
process is mechanistically feasible, the challenge is two-fold.
Firstly, the direct oxidative Heck reaction between 1 and 3 will be
a strong competitive process.[13] Secondly, the oxidant applied to
regenerate the Pd(II) may not be compatible with aryl boronic acid
ortho-C-H activation and
a Pd(II)/norbornene cooperative
catalysis relay mechanism. As can be seen, the emerging Pd(II)-
initiated cooperative catalysis behaved quite differently from the
classical Pd(0) version, thus opening a new avenue for this field.
Aryl boronic acids and their derivatives are widely accessible
and useful organic reagents,[8] which have been extensively
[*]
S. Chen,† Z.-S. Liu,† Y. Hua, Z. Zhou, Dr. H.-G. Cheng, Prof. Dr. Q.
Zhou
College of Chemistry and Molecular Sciences, Wuhan University,
Wuhan, 430072 (China)
E-mail: qhzhou@whu.edu.cn
Homepage: http://qhzhou.whu.edu.cn/
T. Yang, Prof. Dr. Q. Zhou
The Institute for Advanced Studies, Wuhan University, Wuhan,
4
30072 (China)
[†
]
These authors contributed equally to this work.
Supplementary information for this article is given via a link at the
end of the document.
2
, which will result in various side reactions including homo-
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COMMUNICATION
8
Table 1. Optimization of reaction conditions.[
a]
the mediator N had a positive effect on the reaction. For instance,
8
increasing the loading of N to 1.0 equivalent and 1.5 equivalents
provided 4a in 89% and 99% yield respectively (entries 13-14).
Additional optimization of the base, palladium catalyst and the
oxidant did not provide significant improvement in the efficiency
(
see the Supplementary Information (SI) for details). Finally, the
[
b]
optimal conditions involved the reduction of the base to 2.0
Entry
[NBE]
Solvent
Yield [%]
equivalents, which furnished 4a in 99% yield (91% isolated yield)
1
1
2
3
4
5
6
7
8
9
N
NMP
NMP
NMP
NMP
NMP
NMP
40
14
38
27
21
59
[20]
(
entry 15). It is worth mentioning that the current reaction has
2
N
several advantageous aspects, such as the fact that it uses a
3
N
[21]
green oxidant (air) and does not require any phophine ligand
(
4
N
8
N may act as a ligand as well as mediator). Additionally, the
5
N
reaction proceeds well in an open flask at ambient temperature.
These practical features make this reaction amenable for process
chemistry.
With the above optimal conditions identified, we first examined
the scope of aryl boronic acids, with bromide 2a and olefin 3a as
the reaction partners (Table 2). First, we explored the
compatibility of ortho-substituted aryl boronic acids, which would
give mono-alkylated products. As shown in Table 2A, polycyclic
aryl boronic acids (4a-e), as well as substrates bearing a methyl
6
N
7
N
NMP
43
8
N
NMP
toluene
MeCN
DMF
70
0
8
N
8
1
1
1
0
1
2
N
0
8
N
73
79
89
99
8
N
N
DMA
DMA
DMA
DMA
[c]
8
1
3
(
4f, 4j-n), ethyl (4g), phenyl (4i) and even sterically hindered
[d]
8
1
4
N
N
isopropyl group (4h) at the ortho position were suitable substrates,
furnishing the Catellani products in moderate to good yields (58-
[
d,e]
8
[f]
1
5
99 (91)
88%). Other substituents including fluoro (4j and 4m), chloro (4k)
and bromo (4c) at 3- or 4-positions were well-tolerated. Notably,
heteroaryl boronic acid also reacted well to afford the desired
product (4o) in 63% yield. We further investigated the practicality
of this protocol on a larger scale (5 mmol), which led to a gram-
scale preparation of product 4a (1.53 g, 83% yield).
Next, the reactivity of aryl boronic acids without ortho-
substitution were examined (Table 2B). Gratifyingly, these
substrates containing either electron-donating or -withdrawing
groups proved to be competent substrates, providing the
[
a]All reactions were performed on 0.2 mmol scale. [b]GC yield with biphenyl
as an internal standard. [c] 1.0 equiv of N was applied. [d] 1.5 equiv of N8
8
2 3
was applied. [e] 2.0 equiv of K CO was applied. [f] Isolated yield in
parentheses, which is calculated based on the olefin. NMP: N-methyl-2-
pyrrolidinone, DMF: N,N-dimethylformamide, NMA: N,N-dimethylacetamide.
coupling,[14]
deboronation.[15]
oxidation
to
phenols,[15]
and
protolytic
Table 2. Reaction scope with respect to the aryl boronic acid.[a]
To address the aforementioned challenges, our efforts
commenced with the model reaction using readily available 1-
naphthylboronic acid pinacol ester (1a'), ethyl 4-bromobutanoate
(
2a) and tert-butyl acrylate (3a) as the reactants (Table 1).
Pd(OAc) was initially chosen as the catalyst (10 mol%), K CO
2
2
3
as the base (3.0 equiv), and NMP as the solvent, while the
o
reaction was allowed to run at ambient temperature (30 C) under
air (as the mild oxidant)[16] to minimize possible side reactions. To
1
our delight, the reaction with 50 mol% NBE (N ) did furnish the
desired product 4a in 40% yield (entry 1). In attempt to improve
the reaction efficiency, various readily available norbornene
2
derivatives were then examined, including 2,5-norbornadiene (N ),
3
[17]
5
(
-norbornene-2-carboxylic acid (N )
and the Dong mediator
4
[18]
N ) (entries 2-4), which did not improve the efficiency of this
process. Gratifyingly, the inexpensive NBE derivative 5-
norbornene-2-carbonitrile N8 was identified as the optimal
mediator,[ affording 4a in a significantly improved yield (70%)
19]
(
entry 8).Following studies focused on screening reaction solvent,
which plays a critical role in this process. The switching of NMP
for toluene or acetonitrile led to no product formation (entries 9-
10). In contrast, the amide-type solvent DMF behaved similarly to
NMP (Entry 11), while the use of DMA increased the yield of 4a
to 79% (Entry 12). Thus, DMA was selected as the optimal
reaction solvent. Further optimization indicated that the amount of
[
a] All reactions were performed on a 0.2 mmol scale. Reported yields are
for the isolated products, , which are calculated based on the olefin. [b] Ar-
Bpin was used instead of Ar-B(OH) . [c] on 5.0 mmol scale. [d] 2.4 equiv of
alkyl bromide and 3.0 equiv of K CO were applied.
2
2
3
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COMMUNICATION
dialkylated products in moderate to good yields. Notably, the
reaction system also exhibited high chemo-selectivity: various
functional groups were tolerated, including fluoride (4aa), chloride
Compared to the classical Catellani reactions, the different
reaction mechanism and the extremely mild reaction conditions of
the current Borono-Catellani process prompted us to investigate
the possible orthogonal reactivity[26] between them. The readily
available bifunctional reagent 6 containing an iodo and a Bpin
group was chosen as the model substrate. Under classical
Catellani reaction conditions,[27] only trace amount of the Catellani
product 7 was obtained, alongside the intramolecular Suzuki
coupling product 8 as the major component. In sharp contrast, 6
was able to react with 2a and 3a under the standard Borono-
Catellani reaction conditions to afford the Borono-Catellani
product 9 in good yield (67%) with no classical Catellani product
observed, which further demonstrated the excellent chemo-
selectivity of this process. The intact iodo group in 9 enabled a
conventional Catellani reaction to provide the product 10 in 67%
yield. Thus, the orthogonal reactivity between the two types of
Catellani reactions was evidently demonstrated. In addition, 9
could undergo a microwave promoted intramolecular Heck
reaction[28] to form the complex polycyclized product 11 in good
yield. Efforts are underway to utilize this strategy in the
preparation of complex natural products and important
therapeutics.
(
4
4p and 4x), bromide (4q), hydroxy (4r and 4v), methoxy (4s and
aa), benzyloxy (4y), TMS (4t), vinyl (4u) and acyl (4w), providing
handles for further product diversifications. Interestingly, when the
pinacol ester 1z' was tested, the TBS deprotected product 4z was
obtained in 40% yield, indicating the TBS group isn’t compatible
with the reaction conditions. Lastly, it’s found that the pinacol ester
of heteroaryl boronic acids (4ab-ad) were also suitable substrates
to deliver the desired products in moderate yields.
Due to improved stability or ease of preparation, some cases
in Table 2 utilized the corresponding pinacol ester as substrate
instead of the boronic acid,[22] for example, 4d, 4o, 4u, 4x, 4z and
4ab-ad. As to case 4a and 4aa, both the boronic acids and the
corresponding pinacol esters were tested, and the later were
found to give slightly higher yields.
Then, the scope of bromides 2 was examined (Table 3A).[23]
Alkylation with simple ethyl bromide (2b), n-butyl bromide (2c),
alkyl bromides with a long aliphatic chain (2d-e), as well as the
cyclopropyl and phenyl substituted alkyl bromides (2f-g) gave the
desired products in good to excellent yields (77-88%). Bromides
containing an array of functional groups including cyano (2h),
bromo (2i), acetal (2k), amide (2l), and protected amino (2m)
gave good to excellent yields (61-87%). It is noteworthy that a free
hydroxyl group (2j) was also compatible with this protocol.
The scope of olefins 3 was also explored.[24] As shown in Table
3B, an array of mono-substituted olefins with electron-
withdrawing groups are suitable substrates (3a-e), providing the
desired products in good to excellent yields (67-97%).
Interestingly, simple styrene (3f) and 4-nitro-styrene (3g) were
also suitable substrates to afford the products in 46% and 78%
yields, respectively.
Table 3. Reaction scope with respect to the alkyl bromide and olefin.[a]
Scheme 1. Synthetic applications. [a] All reactions were performed on a 0.2
mmol scale. Reported yields are for the isolated products, which are calculated
based on the olefin. [b] reaction temperature was 70 oC. Reagent and
conditions: (1) Pd(OAc)
Pd(OAc) , Ph P, NBE, Cs
NaHCO , Bu NCl, DMF, 130 C, mw, 40 min.
2
, Ph
3
P, NBE, Cs
2 3 3
CO , CH
CN, 90 oC, Ar, 1 h; (2)
CN, 90 oC, Ar, 12 h; (3) Pd(OAc)
2
3
2
CO
3
, CH ,
3
2
o
3
4
In summary, we have developed a Pd(II)-initiated Borono-
Catellani reaction utilizing the widely accessible aryl boronic acids
and derivatives as the substrates instead of aryl halides, thereby
greatly expanding the existing paradigm of this powerful
transformation. The inexpensive reagent 5-norbornene-2-
carbonitrile is used as the mediator for the first time. Practicality
is the salient feature of this Borono-Catellani reaction. It is run
under air at ambient temperature while no phosphine ligand is
needed. This mild, chemo-selective, and scalable protocol is
compatible with a large range of readily available functionalized
aryl boronic acids, bromides as well as terminating olefins.
Moreover, the orthogonal reactivity between the Borono-Catellani
and classical Catellani reactions was demonstrated. We believe
this work should open up new avenues for developing novel
Catellani-type reactions.
[
a] All reactions were performed on a 0.2 mmol scale. Reported yields are
for the isolated product, which are calculated based on the olefin.
To further illustrate the synthetic utility of this protocol, an
annulation process was explored based on a speculated two-
component Borono-Catellani process (Scheme 1A). It was found
that 1a' reacted with the bifunctional reagent 5a[25a] and 5b
bearing a bromide and an olefin group, to afford the benzo-fused
products 4a'' and 4b'' in 61% and 68% yields, respectively. A
higher reaction temperature was needed for the latter to obtain a
reasonable yield. Thus, the two-component Borono-Catellani
process provides an attractive method complementary to the
existing Catellani-type annulations.[25]
Acknowledgements
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Angewandte Chemie International Edition
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COMMUNICATION
We are grateful to the National Key Research and Development
Program of China (No. 2016YFB0101203), the National “1000-
Youth Talents Plan”, the Innovation Team Program of Wuhan
University (Program No. 2042017kf0232) and start-up funding
from Wuhan University for financial support. We thank Prof. Wen-
Bo Liu (Wuhan University) for sharing the instruments, Prof. P.
Andrew Evans (Queen’s University) for helpful discussions, Prof.
Wenjun Tang (Shanghai Institute of Organic Chemistry) and Dr.
Ming Yan (Fish & Richardson) for assistance with the preparation
of the manuscript.
[11] For selected examples, see: a) M. Catellani, E. Motti, M. Minari, Chem.
Commun. 2000, 157; b) T. Wilhelm, M. Lautens, Org. Lett. 2005, 7, 4053.
[
12] During the preparation of this manuscript, an elegant similar
transformation was reported by the Zhang group, see: G.-F. Shi, C.-D.
Shao, X.-T. Ma, Y.-C. Gu, Y.-H. Zhang, ACS Catal. 2018, 8, 3775. In this
work, they described a similar three-component Borono-Catellani reaction
utilizing aryl boronic acids, alkyl iodides and olefins as the substrates. The
main difference between these two works lies in the optimal reaction
conditions used.
[
[
13] a) T. Kurahashi, H. Shinokubo, A. Osuka, Angew. Chem. Int. Ed. 2006,
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Keywords: Catellani reaction • norbornene • cooperative
catalysis • aryl boronic acid • air • orthogonal reactivity
[
[
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[
[
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19] N is an inexpensive reagent, and the price is just 1.5 $/gram (from Energy
Chemical).
20] If 1.0 equivalent of 1a' was applied under the optimal conditions, the yield
of 4a dropped to 60% GC yield accordingly.
21] For selected phosphine ligand-free cases, see: a) M. Catellani, E. Motti,
M. Minari, Chem. Commun. 2000, 157; b) M. Catellani, E. Motti, S. Baratta,
Org. Lett. 2001, 3, 3611; c) E. Motti, F. Faccini, I. Ferrari, M. Catellani, R.
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[
[
[
[
[
22] The reactivity of various ary boronic acid derivatives, including the
Molander salt was checked, and the results were described in SI, part 10.
23] Reactions with secondary alkyl bromide suffered from low yields or even
no reactivity under the current conditions.
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24] Some suitable olefins in Zhang’s work (Ref. 12), like phenyl vinyl sulfone,
and allyl acetate suffered from low yields under the current conditions,
which may result from the low reaction temperature.
[
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Shuqing Chen , Ze-Shui Liu , Tao Yang,
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The Discovery of A Pd(II)-Initiated
Borono-Catellani Reaction
A Pd(II)-initiated Borono-Catellani reaction utilizing widely accessible aryl boronic
acids as the substrates instead of aryl halides was developed. The reaction was
promoted by cooperative catalysis of Pd(OAc)
2
and the inexpensive 5-norbornene-
2-carbonitrile. Practicality is the salient feature of this reaction: It is run under air at
ambient temperature while no phosphine ligand is needed. This mild, chemo-
selective, and scalable protocol is compatible with a large range of readily available
functionalized aryl boronic acids, bromides as well as terminating olefins (50
examples, 39-97% yields). Moreover, the orthogonal reactivity between the Borono-
Catellani and classical Catellani reaction was demonstrated.
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