Nickel-Catalyzed Highly Selective Hydroalkenylation of Alkenyl Boronic Esters to Access Allyl Boron

Article abstract of DOI:10.1021/acs.orglett.0c02923

Allyl boron derivatives are valuable building blocks in the synthesis of natural products and bioactive molecules. Herein, a practical strategy of nickel-catalyzed highly selective hydroalkenylation of alkenyl boronic esters was developed. Under the mild

Full text of DOI:10.1021/acs.orglett.0c02923

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Letter
Nickel-Catalyzed Highly Selective Hydroalkenylation of Alkenyl
Boronic Esters to Access Allyl Boron
Penglin Zhang, Min Zhang, Yuqi Ji, Mimi Xing, Qian Zhao, and Chun Zhang*
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ABSTRACT: Allyl boron derivatives are valuable building blocks
in the synthesis of natural products and bioactive molecules.
Herein, a practical strategy of nickel-catalyzed highly selective
hydroalkenylation of alkenyl boronic esters was developed. Under
the mild reaction conditions, a variety of allyl boronic esters were
accessed with excellent chemo- and regioselectivity. The
mechanism of this transformation was illustrated by control
experiments and kinetic studies.
contain an alkene group (3, Scheme 1). So this kind of
sing relatively simple and readily accessible precursors to
Umake synthetically valuable products has benefitted the research is important for both exploring the selective
research of organic synthesis.1 Recently, the transition-metal-
functionalization of olefin and developing a practical strategy
for the synthesis of allyl boronic ester. Herein, we developed a
novel method to realize Ni-catalyzed regioselective hydro-
alkenylation of alkenyl boronic esters.
catalyzed functionalization of vinyl boronate, which could offer
the attractive alternative to traditional boronate reagent
making, has caught more and more attention.2,3 A series of
elegant works has proved that complex benzyl and normal alkyl
boronates could be synthesized by hydroalkylation (1, Scheme
1),4 hydroarylation (2, Scheme 1),4a,5 and difunctionalization6
of alkenyl boronic ester. However, the parallel strategy to make
allylic boronic compounds, which are a class of versatile
reagents, is still not realized. As shown in Scheme 1, the
obvious challenge of this transformation is how to control the
chemoselectivity, as both the starting materials and product
Because of the utility of allyl boronic reagents in organic
synthesis,7,8 their preparations have been studied intensively in
recent decades.9,10 For example, the Aggrawal group has
developed an elegant protocol to make allylboron reagents
from vinyl boronic esters and organic lithium reagents.11
Without stoichiometric organometal reagents, the present
method employed Ni hydride as catalyst,12 which could
improve the functional-group tolerance. On the basis of the
different kinetics of the Ni−H species inserted into three kinds
of alkenes, we developed a practical method to prepare
allylboron reagents from a vinyl boronic compound with good
substrate scope.
Scheme 1. Synthesis of Allylboronates from Alkenyl Boronic
Esters
Our study commenced with the nickel-catalyzed reaction of
alkenyl boronic ester 1a, alkenyl triflate 2a, and poly-
(methylhydrosiloxane) (PMHS).13 Interestingly, the above
reaction gave the desired product 3a with 33% yield (Entry 1,
Table 1; yield determined by gas chromatography (GC)). We
then surveyed the effect of different silanes. Compared with
PMHS, some other silanes afforded much better results
(Entries 1 and 2, Table 1 and Supporting Information).
Especially, when (EtO)3SiH was chosen, the product could be
given with 63% yield (Entry 2, Table 1). Further investigation
Received: September 1, 2020
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© XXXX American Chemical Society
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a
a
Table 1. Effects of Different Reaction Conditions
Table 2. Scope of Different Alkenes (1)
a
1a (0.2 mmol), 2a (0.4 mmol), [Ni] (0.01 mmol), ligand (0.012
mmol), base (0.4 mmol), silane (0.4 mmol), solvent (1.5 mL), at 25
b
°C for 24 h. Yields determined by GC using n-dodecane as the
c
internal standard. Isolated yield.
suggested that other kinds of bases could not afford better
results (Entries 3 and 4, Table 1). Notably, this reaction was
sensitive to the solvent (Entries 5−7, Table 1 and Supporting
Information). After the screening, the mixed solution of
dimethylacetamide (DMA) and CH3CN was selected as the
best choice, which could improve the yield of a desired product
remarkably (Entry 7, Table 1). Then, the effect of different
nickel catalysts was studied. Compared with NiBr2·diglyme,
other kinds of Ni salts induced lower yields (Entries 8−10,
Table 1). Further studies indicated different kinds of ligands
could affect the results of this reaction obviously (Entries 11
and 12, Table 1). Among them, L1 was the best one. Finally,
the condition of entry 7 was chosen as the optimal condition.
With the optimal reaction condition in hand, the substrate
scope of different alkenes was investigated (Table 2). In
general, various alkenyl boronic esters and unactivated boron-
containing alkenes resulted in a diversity of allylboron esters
with modest to good yields and high regioselectivity. As shown
in Table 2, alkenyl boronic ester substrates, which were
installed with chloro, ether, ester, nitrile, and amide groups,
worked very well (4c to 4k, Table 2). The corresponding
products of these starting materials could be used for further
transformations. Besides 4,4,5,5-tetramethyl-1,3,2-dioxaboro-
nate-type alkenyl boronic esters, further studies indicated that
4,4,6,6-tetramethyl-1,3,2-dioxaboronate and 2,3-dihydro-1H-
naphtho[1,8-de][1,3,2]diazaboronate version substrates still
worked well (4l and 4m, Table 2). Importantly, unactivated
terminal and internal boron-containing could go through the
chain-walking-type reaction to afford the desired allylboron
esters (4o to 4r, Table 2).14
a
Standard conditions: 1 (0.2 mmol), 2a (0.4 mmol), Ni Br2·diglyme
(0.01 mmol), L1 (0.012 mmol), KF (0.4 mmol), (EtO)3SiH (0.4
b
mmol), DMA/CH3CN (30:1) (1.5 mL), at 25 °C for 24 h. Isolated
yield. The detailed oxidation process is shown in the Supporting
Information. NMR yield of corresponding boride.
c
d
both alkenyl triflates and alkenyl bromide substrates proceeded
well with excellent regioselectivity (Table 3). Cyclic alkenyl
triflates with -Me, -F, -Ph, or -tBu could be tolerated with this
catalyzed reaction condition (5b to 5e, Table 3). Notably,
alkenyl bromides could be compatible with the reaction, and
starting materials with ortho-, meta-, or para-substituents at the
arene group could be converted into the desired product
smoothly (5f to 5i, Table 3). Further studies suggested the
benzene ring with an electron-donating group or an electron-
withdrawing group did not affect the efficiency of this
transformation (5j to 5m, Table 3). Importantly, the pyridine,
furan, and naphthyl motifs could survive (5n to 5p, Table 3).
The potentiality for a pharmaceutical molecule modification of
this reaction was well-demonstrated by these results.
The substrate scope of the nickel-catalyzed highly selective
hydroalkenylation transformation was further expanded to a
variety of alkenyl electrophiles 2. These results indicated that
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a
benzaldehyde to obtain the alcohol 8 with good yield (d,
Scheme 2).
Table 3. Scope of Different Alkenyl Reactants (2)
To elucidate the possible reaction mechanism, several
control experiments were designed. First, a mixture of olefinic
isomers could be transformed smoothly into a single product
4b under the standard condition, which manifested the good
regioconvergent hydroalkenylation of this method (eq 1,
Scheme 3). In the presence of butylated hydroxytoluene
Scheme 3. Control Experiments
(BHT), the reaction was not inhibited (eq 2, Scheme 3). This
result suggested a radical intermediate might not be involved in
the reaction processes. When 1a was replaced by 9, the
compound 10 could not be detected in the reaction system,
which demonstrated alkylsilane 9 should not be the
intermediate of this chemistry (eq 3, Scheme 3). Furthermore,
the crossover experiments using a mixture of deuterium-labeled
olefin and undeuterated olefin were performed. The result
suggested no H/D scrambled crossover products were
obtained (Supporting Information). Therefore, no NiH
dissociates from one olefin and reassociates with another
olefin during the chain-walking process.
a
Standard conditions: 1a (0.2 mmol), 2 (0.4 mmol), NiB r2·diglyme
(0.01 mmol), L1 (0.012 mmol), KF (0.4 mmol), (EtO)3SiH (0.4
b
mmol), DMA/CH3CN (30:1) (1.5 mL), at 25 °C for 24 h. Isolated
c
yield. Diastereomeric ratio (dr) determined by GC−mass spectrom-
etry or high-performance liquid chromatography analysis.
Interestingly, the reaction could be performed at the gram
scale to afford 3a with a 66% yield (a, Scheme 2). The
To get more information on the mechanism, the dynamics
parameter of 1a, 2a, and 3a reacted with stoichiometric NiH
species were studied, respectively. The monitoring of kinetic
experiments clearly illustrated the relative reaction rates of
three kinds of alkenes with the NiH species (Figure 1). As
shown in the curve, the concentration of 1a decreased much
faster than the concentration of others, which suggested 1a
Scheme 2. Gram-Scale Reaction and Synthetic
Transformations
products of this chemistry are a kind of versatile intermediate
for chemical synthesis. As shown in Scheme 2, the product 3a
could go through a two-step oxidation reaction to make α,β-
unsaturated ketone 6 with 62% yield (b, Scheme 2).
Furthermore, homoallylic alcohol 7 could be synthesized
from 3a by a well-established reaction (c, Scheme 2).
Moreover, the product 3a easily went through reaction with
Figure 1. Kinetics studies.
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Authors
reacted with the NiH species much more easily than did the
others. The above essence could avail the desired reaction
steps. Importantly, the data of 3a reacted with the NiH species
suggested that the product could be intact in this chemical
system. The nature of the dynamics ensured the present
chemistry worked smoothly.
Penglin Zhang − Institute of Molecular Plus, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University, Tianjin
300072, China
Min Zhang − Institute of Molecular Plus, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University, Tianjin
300072, China
Yuqi Ji − Institute of Molecular Plus, Tianjin Key Laboratory of
Molecular Optoelectronic Science, Department of Chemistry,
School of Science, Tianjin University, Tianjin 300072, China
Mimi Xing − Institute of Molecular Plus, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University, Tianjin
300072, China
On the basis of the above studies, a possible mechanism of
this transformation was illustrated in Scheme 4. The active
Scheme 4. Proposed Reaction Mechanism
Qian Zhao − Institute of Molecular Plus, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University, Tianjin
300072, China; orcid.org/0000-0003-0408-0864
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c02923
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from Tianjin University and the National
Natural Science Foundation of China (No. 21801181) is
acknowledged.
LNiH (I) species was generated as the first step of this
transformation.15 It inserts into alkenes to form the alkyl Ni
intermediate (II), and then it proceeds via chain walking by a
sequence of reversible β-H elimination and reinsertion to
afford the alkylnickel intermediate (V).16 The NiIII inter-
mediate (VI) could be generated from the reaction of V and
2.16 After it goes through a reductive elimination, VI could be
converted into allylboron derivatives 3.
In conclusion, we have developed a practical strategy for the
synthesis of allylboron derivatives, which are valuable synthetic
intermediates for organic synthesis, by nickel-catalyzed hydro-
alkenylation of alkenyl boronate. Under the mild reaction
condition, a series of allyl borate esters have been accessed,
with excellent chemo- and regioselectivity. Furthermore, the
mechanism of this transformation was illustrated by control
experiments and kinetic studies. Further studies on enantio-
selective tansformation and synthetic applications are ongoing
in our laboratory.
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ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c02923.
Experimental procedures, details of experiment, and
spectral data (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Chun Zhang − Institute of Molecular Plus, Tianjin Key
Laboratory of Molecular Optoelectronic Science, Department of
Chemistry, School of Science, Tianjin University, Tianjin
300072, China; orcid.org/0000-0001-6848-2868;
Email: ChunZhang@tju.edu.cn
D
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