Transition-Metal-Free Deaminative Vinylation of Alkylamines

Article abstract of DOI:10.1002/adsc.201900576

The amino group is one of the most fundamental structural motifs in natural products and synthetic chemicals. However, amines potential as effective alkylating agents in organic synthesis is still problematic. A unified strategy has been established for deaminative vinylation of the alkylamines with vinyl boronic acids by C?N bond activation under catalyst-free conditions. The key to the high reactivity is the utilization of pyridinium salt-activated alkylamines, with a base as a promoter. The transformation exhibits good functional group compatibility, and includes inexpensive primary amine feedstocks and amino acids. The proposed method can serve as a powerful synthetic method for late-stage modification of complex compounds. Mechanistic experiments suggest that free radical processes are involved in this system. (Figure presented.).

Full text of DOI:10.1002/adsc.201900576

Title: Transition-Metal-Free Deaminative Vinylation of Alkylamines
Authors: Jiefeng Hu, Bo Cheng, Xianyu Yang, and Teck-Peng Loh
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Transition-Metal-Free Deaminative Vinylation of Alkylamines
Jiefeng Hu,a* Bo Cheng,a Xianyu Yang,a Teck-Peng Loha, b*
a
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic
Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China
E-mail: iasjfhu@njtech.edu.cn
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang
b
Technological University, Singapore 637371, Singapore
E-mail: teckpeng@ntu.edu.sg
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract: The amino group is one of the most fundamental
structural motifs in natural products and synthetic
chemicals. However, amines potential as effective
alkylating agents in organic synthesis is still problematic. A
unified strategy has been established for deaminative
vinylation of the alkylamines with vinyl boronic acids by
C−N bond activation under catalyst-free conditions. The
key to the high reactivity is the utilization of pyridinium
salt-activated alkylamines, with a base as a promoter. The
been made in transition metal-free coupling of alkenyl
or aryl boronic acids in a stable, nontoxic, and
environmentally friendly fashion. Tang developed the
first metal-free cross-coupling between benzyl/allyl
halides/mesylates and alkenylboronic acids via an SN2-
type process in 2016 (Figure 1a)[8]. In light of these
reported advances, efforts towards exploring metal-
free cross coupling of easily available alkyl sources are
still important for organic synthesis because new
strategies would provide innovative inspiration for the
synthesis of complex natural products and other
bioactive molecules.
transformation
exhibits
good
functional
group
compatibility, and includes inexpensive primary amine
feedstocks and amino acids. The proposed method can
serve as a powerful synthetic method for late-stage
modification of complex compounds. Mechanistic
experiments suggest that free radical processes are involved
in this system.
Keywords: alkylamines; deaminative transformations;
olefins; catalyst-free
Over the few decades, transition-metal catalysed
cross-coupling
reactions,
in
particular,
Suzuki−Miyaura coupling, have been of fundamental
interest and played an im-portant role in the synthesis
of complex organic molecules.[1] Despite the
revolutionary advances of C(sp2)−C(sp2) cross-
couplings, alkyl-Suzuki coupling reactions are much
less developed due to issues related to β-hydride
elimination and challenging oxidative addition.[2] In
general, different kinds of transition-metal catalysts,
mainly palladium[3], nickel[4], copper[5], and iron[6]
complexes, have been successfully used for the
construction of C(sp2)−C(sp3) bonds via Suzuki
couplings. By contrast, metal-free cross couplings of
sp3-hybridized carbon electrophiles have drawn
interest in an effort due to avoid transition metal
residues in the synthesis of biologically active
compounds.[7] In particular, impressive progress has
Figure 1 Development of a catalyst-free system for
deaminative transformations of Katritzky pyridinium salts.
a) Transition-metal-free coupling with alkenylboronic acids;
b) catalyst-free photoin-duced deaminative transformations;
c) transition-metal-free deam-inative vinylation. Using 3-
Borylated Indoles as the Building Blocks.
Amines are widely found in naturally-occurring and
syn-thetic compounds, and are poor electrophiles
because of the resonance stability of the C−N bond.
Tremendous progress has been made in the
development of transition metal-mediated/catalysed
1
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
o
cross coupling reactions via the cleavage of C(sp2)−N At a lower temperature of 60 C (entry 10), the results
bonds in recent years.[9] However, deaminative cross- were found to be slightly inferior than those observed
coupling of alkyl amines has been much less examined under the optimal conditions. When the reaction was
owing to the higher bond energy of C(sp3)−N bonds. performed at room temperature, it resulted in poor
The chemical bond energy of inert C(sp3)−N could be conversion (entry 11). Finally, the reaction could be
effectively reduced by the conversion of primary alkyl conducted in the dark, indicating it is not a visible-
amines into pyridinium salts, known as “Katritzky light-driven deaminative functionalization (entry 12).
salts”.[10] Recently, radical- mediated transformations
Table 1 Optimizaion the reaction conditions.[a]
of these redox active amines have attracted broad
attention among chemists. In 2017, the Watson[11] and
Glorius[12] groups reported that Katritzky salts can act
as alkylating agents in radical-induced deaminative
arylation by using metal catalysts. Recently, the
deaminative alkyl-Heck-type reaction of alkyl amines
was developed utilizing visible-light photoredox
Entry Variation from the standard conditions Yield (%)b
catalysis[13]. These novel transformations usually rely
1
2
none
without base
85 (78)c
on metal catalysis or photolysis to promote single-
electron transfer (SET)-induced deamination[14]
.
0
Noteworthily, cross-couplings of benzylic pyridinium
salts and vinylboronic acids have been reported by
Watson’s group including low-yielding, metal-free
examples.[14a] In addition, Aggarwal[15] and our
group[16] have demonstrated a transition-metal-free
system for selective borylation of alkylamine C−N
bonds via single-electron transfer (SET)-induced
deamination under mild conditions. Inspired by these
advances and following our interest in the activation of
inert C−N, we envisioned that Katritzky salts as
electrophiles could undergo a cross-coupling reaction
with alkenyl boronic acids under metal-free catalytic
conditions. While this manuscript was under
preparation, Aggarwal reported a general catalyst-free
deaminative functionalization of primary amines via
photoinduced SET[17] (Figure 1b). Herein, we report
our results on the utilization of pyridinium salt-
activated alkylamines as the alkylating component in a
base-promoted deaminative vinylation reaction (Figure
1c).
3
Using Et3N instead of DBU
Using K3PO4 instead of DBU
Using CsOAc instead of DBU
Using KOH instead of DBU
DMF
39
4
28
5
48
6
60
7
51
8
THF
36
9
toluene
at 60 oC
16
10
11
12
63
at room temperature
in the dark
33
81
[a] Reaction conditions: 1b (0.20 mmol), 1c (0.30 mmol), and 2.0
equiv of DBU in DMA (1.0 mL), 10 h, under Ar. [b] Determined by
GC
Diazabicyclo[5,4,0]undec-7-ene, DMA = N, N-dimethylacetamide,
DMF = N, N-dimethylformamide.
[c]
analysis.
Isolated
yield.
DBU
=
1,8-
With this exciting initial result in hand, we
proceeded to investigate the broad scope of Katrizky
salts that had been prepared from the corresponding
primary alkyl amines (Table 2). As shown, cyclic
amine substrates were efficiently transformed into the
corresponding alkenylation products (2d-6d). In
particular, the substrate 4d, which has an internal
alkenyl motif, and fluorine-containing substrate 5d
worked well under the optimized procedure. The olefin
products from reactions resulting in substituted
phenolic ester (7d) and silyl ether (8d) were formed at
a good yield. Under our conditions, substrates
containing active hydrogen were also compatible
(9d−12d). Excitingly, the reaction of hydroxyl-
containing substrate 10b afforded 10d at a 67% yield
with excellent diastereoselectivity. Importantly, the
tertiary amine 13b could also be converted into the
desired product 13d at a 63% yield. Unfortunately,
We began our investigations by monitoring the
reactivity of the pyridinium salt (1b) derived from a
primary amine (1a) with (E)-styrylboronic acid (1c)
under metal-free conditions (Table 1). The reaction
was found to be facile with 1.5 equiv of 1c in the
o
presence of DBU (2.0 equiv) in DMA at 80 C which
afforded the (E)-(2-cyclohexylvinyl)benzene (1d) at a
78% isolated yield, with no observance of the Z
isomers (entry 1). Moreover, the reactions were carried
out on 2.0 mmol scale, which afforded 1d at a 71%
isolated yield. With control experiments performed in
the absence of the base, the reaction was unsuccessful
(entry 2). Other bases, such as Et3N, K3PO4, CsOAc
and KOH, were also effective for this transformation,
albeit with lower yields (entry 3-6). Using DMF or
THF as the solvent led to lower yields (entry 7-8). The
reaction was less efficient in toluene as well (entry 9).
2
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
Table 2 Substrate scope of alkyl amines[a]
[a]
Reaction conditions: A mixture of Katritzky salts b (0.20 mmol), alkenyl boronic acids c (0.30 mmol) and DBU (0.4
mmol) in DMA (1 mL) was stirred for 10 h at 80 °C under Ar, isolated yield after chromatography. [b] Katritzky salts b
(0.20 mmol), alkenyl boronic acids c (0.30 mmol), 2.0 equiv CsOAc in THF (1 mL) under room temperature for 10 h.
pyridinium salts from sterically hindered tertiary
amines, such as adamantyl amine, could not be
prepared. Subsequently, a variety of Katritzky salts
derived from natural and unnatural amino acid methyl
esters were tested. The yield of 14d was decreased to
a 43% yield under standard conditions. When CsOAc
was added as the base, we achieved a better yield,
which was improved up to 80% in THF at room
temperature. As shown, a wide range of electronically
and sterically diverse arenecarboxylic acid esters
underwent cross coupling with 1c at moderate to
excellent yields (15d-25d). The styrene derivatives
contained a wide array of functional groups including
fluorine (15d), chlorine (16d), olefin ester (17d),
cyano (18d), ethanesulfonate (19d), ester (20d) and
phenol (21d), which can be tolerated and synthesized
at 67–83% yields. Furthermore, the sulfur-containing
substrates 22b and 23b were found to be compatible
with the reaction conditions. The couplings of
substrates with heterocyclic aromatic motifs such as
thiophene (24d), and indole (25d) were also tolerable.
To show case the utility of the transformation for
diversifying natural product amines, we prepared a
diverse collection of Katritzky pyridinium salts and
subjected them to the optimized reaction conditions.
For example, the 5α-cholestan-3-one derivative 26b
could undergo C−N vinylation with (E)-(4-
methoxystyryl)boronic acid to produce 26d at a 64%
yield. Synthesis of the complex molecule 27d was
also successful from mesterolone through a sequence
of reductive amination and activation, followed by
deaminative vinylation at an acceptable yield. In
addition, late-stage modification of the tigogenin
derivative 28b was olefinized with excellent
diastereoselectivity. In addition，we tried several
primary alkyl amines under standard conditions. Only
benzylamine substrates could react with vinyl boronic
3
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
acids, and the yield of (E)-prop-1-ene-1,3-
diyldibenzene was 57.9%.
through a radical pathway (Figure 2). Reagents 1b
and 1c were individually investigated by in situ EPR
in the presence of DMPO. When only substrate 1b
was heated at 80 °C in DMA in the presence of
DMPO, a similar EPR signal was observed. This
result suggested that the reaction might be initiated
by the formation of a new radical from 1b. However,
we cannot distinguish the radical type in the reaction
by EPR.[18]
Table 3 Substrate scope of organoboronic acids[a]
[a]
Reaction conditions: A mixture of Katritzky salts b
(0.20 mmol), alkenyl boronic acids c (0.30 mmol) and
DBU (0.4 mmol) in DMA (1 mL) was stirred for 10 h at 80
°C under Ar, isolated yield after chromatography.
The reaction was further evaluated using Katritzky
salts (b) in conjunction with a more diverse pool of
organoboronic acids (c). As shown in Table 3, a wide
range of substituted styrylboronic acids that
incorporate electron-neutral, electron-donating, and
electron- withdrawing substituents were readily
tolerated (29d-40d). Among them, the substrate
bearing a BocNH group afforded the desired product
at an excellent yield (38d). For the substrate with a
thiophene substituent, product (40d) was generated at
good yields (74%). We believed that the high
functional group tolerance was due to the fact that the
only reagent used was a base.
Figure 3 Mechanistic studies.
To gain deeper insights into the reaction
mechanism, several experiments were conducted.
Under standard conditions, cross coupling of 29b,
prepared from (S)-3-aminotetrahydrofuran, resulted
in racemic 41d (Figure 3). Additionally, radical
inhibiting experiments were carried out in the
presence of radical traps. The reaction was
completely inhibited in the presence of TEMPO
(2,2,6,6-tetramethylpiperidine-1-oxyl), resulting in
the formation of the alkylated TEMPO derivative
41d’, which was detected by GC-MS and NMR.
These results demonstrated that this reaction proceeds
through a radical process. To further corroborate this
hypothesis, reaction of the pyridinium salt 29b with
1,1-diphenylethylene was performed. Expectedly, the
reaction proceeded under standard conditions, leading
to the formation of product 41d’’ at a 28% GC yield.
On the basis of these investigations and our work,
a possible mechanism is proposed in Figure 3. The
Katritzky salts could form an alkyl radical I, which
then triggers a SET process by a thermal event. The
radical I is intermolecularly trapped by a vinyl
boronic acid, giving the corresponding radical II.
This formation is presumably the reason why the
EPR spectrum of the reaction mixture is very
complex. Radical II is then oxidized by pyridinium
Figure 2 EPR spectra: (A) Standard reaction at 80 °C for
4 h; (B) Standard reaction with DMPO at 80 °C for 4 h; (C)
1b and DMPO; (D) 1c and DMPO;
To investigate the reaction mechanism, reactions
between Katrizky salts 1b and alkenyl boronic acids
1c in DMA were investigated by in situ EPR using
5,5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin
trap. In the absence of DMPO, the EPR spectrum of
the reaction mixture, involving 1b and 1c in DMA at
80 °C for 4 h, showed no signal. However, in the
presence of DMPO, complex EPR signals arising
from different spin adducts were detected at g =
2.007 with AN = 14.1 G and AβH = 21.9 G,
suggesting that the catalytic reaction proceeded
4
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
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a
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In summary, we developed an efficient metal-free
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Katritzky pyridinium salts derived from diverse
alkylamines for deaminative vinylation to produce
various olefins. This transformation showed
exceptional functional group tolerance, high
efficiency, and excellent chemoselectivity. In view of
the widespread utility of the amine group, this
method offers a very meaningful tool in synthetic
transformation. We anticipate that the strategy
developed here may provide inspiration for the design
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Experimental Section
General
Procedure
for
Transition-Metal-Free
Deaminative Vinylation of Alkylamines:
Flame-dried 10 mL Schlenk tube filled with argon, 1-
cyclohexyl-2,4,6-triphenylpyridin-1-ium tetrafluoroborate
(95.4 mg, 0.2 mmol) (1b), (E)-styrylboronic acid (44.4 mg,
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0.3 mmol) (1c), absolutely dry DMA (1 mL) and DBU
(60.8 mg, 0.4 mol, 2 equiv) was added. The reaction
mixture was stirred for 10.0 hours at 80 oC. DCM (10 mL)
was added into reaction mixture, and then concentrated in
vacuo. The crude product was purified by column
chromatography on silica gel (200-300 mesh) (eluent: EA /
PE from 1 : 50 to 1 : 20) to afford the corresponding
product.
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,
Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (21901114), the Natural Science
Foundation of Jiangsu Province (BK20180685), the Natural Sci-
ence Foundation of Jiangsu Provincial Department of Education
(18KJB150017), and the Start-up Grant from Nanjing Tech Uni-
versity (38274017102 and 39837101) for financial support. The
SICAM Fellowship by Jiangsu National Synergetic Innovation
Center for Advanced Materials is also acknowledged.
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6
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10.1002/adsc.201900576
Advanced Synthesis & Catalysis
COMMUNICATION
Transition-Metal-Free Deaminative Vinylation of
Alkylamines
Adv. Synth. Catal. Year, Volume, Page – Page
Jiefeng Hu,a* Bo Cheng,a Xianyu Yang,a Teck-
Peng Loha, b*
7
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