(Salen)Mn(III)-catalyzed chemoselective acylazidation of olefins

Article abstract of DOI:10.1039/c8sc01882k

We describe a (salen)Mn(iii)-catalyzed three-component reaction of aldehydes, olefins, and sodium azide for the installation of two useful groups (C═O and N₃) into the double bond. Traditionally, (salen)Mn(iii) in conjunction with iodosobenzene is a classical catalysis system for epoxidation of olefins. Owing to the highly competitive oxygenation approaches, it is a true challenge to establish a distinct strategy for the exploration of new olefin transformations based on this (salen)Mn(iii) catalysis system. Herein, the key to this (salen)Mn(iii)-catalyzed acylazidation of olefins was the rational application of the distinct reactivity of oxomanganese(v) species which is capable of abstracting a hydrogen atom from a substrate C-H bond. This chemoselective reaction occurred in a precisely designed reaction sequence and tolerates complex molecular structures.

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(Salen)Mn(III)-catalyzed chemoselective acylazidation of olefins
Liang Zhang, Shuya Liu, Zhiguo Zhao, Hongmei Su, Jingcheng Hao, and Yao Wang*
Received 00th January 20xx,
Accepted 00th January 20xx
We describe a (salen)Mn(III)-catalyzed three-component reaction of aldehydes, olefins, and sodium azide for the
3
installation of two useful groups (C=O and N ) into the double bond. Traditionally, (salen)Mn(III) in conjunction with
DOI: 10.1039/x0xx00000x
iodosobenzene is a classical catalysis system for epoxidation of olefins. Owing to the highly competitive oxygenation
approaches, it is a true challenge to establish a distinct strategy for the exploration of new olefin transformations based on
this (salen)Mn(III) catalysis system. Herein, the key to this (salen)Mn(III)-catalyzed acylazidation of olefins was the rational
application of different reactivity of oxomanganese(V) species which is capable of abstracting a hydrogen atom from a
substrate C-H bond. This chemoselective reaction occurred in a precisely designed reaction sequence and tolerates
complex molecular structures.
www.rsc.org/
Introduction
A. (salen)Mn(III)-catalyzed transformation of olefins.
Catalytic transformation of olefins is one of the fundamental
approaches for the generation of molecular complexity and
diversity. A range of elegant and powerful strategies have
been established for the installation of a diverse array of useful
functional groups into the double bonds, which essentially
competitive
reactants
(
salen)Mn(III)
(salen)Mn(III)
R1 R3 Oxidant (PhIO, etc.)
RH + R'M
O
Oxidant (PhIO, etc.)
R'
R
R1
2
R
2
R1 R3
R2 R3 classical approach
R
unknown transformations
1
advanced the art and practical use of organic synthesis.
Amongst various catalysts for olefin transformations,
manganese Schiff-base complexes have been well-established
as powerful catalysts for epoxidation of olefins in the last three
B. New strategy: rational application of different reactivity of oxomanganese(V) species
R1 R3
R1 R3
R' R'M + OH
R2
O
Mn
+
R2
R
Mn
Mn
R'
2
R
2
-5
(
Mn(III)+PhIO)
2
R
R
decades . It has been a general notion that the in situ
R-H
+
R'M
R
+
OH
Mn
R3
R3
R1
selective
radical rebound
R1
selective
selective
radical addition
generated oxomanganese(V) species through oxidation of
C-H abstraction
R' rebound
(
salen)Mn(III) complex is an efficient oxygen-transfer species
OH
Mn
epoxidation
radical rebound
OH rebound
6
for epoxidation of various olefins . Owing to the fast and
-7
suppressed
competitive
outcomes
O
R1
R2
R-OH
HO
2
R
5
-7
strong oxygenative background reactions , it remains a
substantial challenge to develop a distinct strategy from a
fresh vision that enables the discovery of previously unknown
olefin transformation based on this oxidative (salen)Mn(III)
catalysis system. (Figure 1A).
R3
R
R1
R3
Figure 1 (Salen)Mn(III)-catalyzed competitive transformation of
olefins.
in Figure 1B, we envisioned that the addition of a carefully
selected reactant bearing a weak C-H bond to the oxidative
The reactive oxomanganese(V) species can readily abstract
a hydrogen atom from even inert C-H bonds such as alkanes to
(salen)Mn(III) catalysis system would lead to a preferential C-H
generate
a
substrate-derived
radical
and
a
abstraction, thus shutting down the highly competitive
epoxidation pathway. Considering the fast radical rebound
hydroxomanganese(IV) intermediate under mild reaction
8
-9
conditions . This distinct reactivity of oxomanganese(V)
species provides a basis point and opens up new opportunities
1
0-11
pathway
, it is essential that the in situ generated radical
must be capable of immediately reacting with the ‘spectator’
olefin to start the precisely designed reaction sequence
towards the desirable outcome. Finally, a selective radical
rebound reaction would finish the whole reaction sequence. A
standing challenge for implementing the designed strategy has
for the development of
a
useful strategy enabling
transformation of olefins from a fresh perspective. As outlined
School of Chemistry and Chemical Engineering & Key Laboratory of the Colloid
and Interface Chemistry, Shandong University
been the suppression of these consecutively competitive
12-13
2
7 Shanda Nanlu, Jinan 250100, Shandong, China
E-mail: yaowang@sdu.edu.cn.
Electronic Supplementary
DOI: 10.1039/x0xx00000x
approaches
.
Information
(ESI)
available.
See
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a
In contrast to alkanes, aldehydes have weaker (O=)C-H Table 1 Optimization of reaction condition
1
4-
bond which can be feasibly cleaved to generate acyl radicals
1
5
(salen)Mn(III) C (2 mol%)
PhIO (3.0 equiv)
N3
O
O
.
Hydroacylation of olefins using aldehydes as an acyl source
represents a simple and efficient method for the preparation
+
Ph
+
n-PrCHO
2a
+
NaN3
Ph
n-Pr
Ph
1
a
solvent, rt, N
2
3a
1
5-18
of ketones
.
Under substantially different reaction
pathways, aldehydes have been applied in acylation of highly
1
9-22
23-28
electron-deficient olefins
or unactivated olefins
.
Despite the important achievements in radical acylation of
olefins, there are considerable limitations that remain to be
1
9-22
resolved with regard to scope of aldehydes and olefins
. At
room temperature, acyl radicals are generally reactive towards
addition of highly electron-deficient olefins while they show
very poor or no reactivity towards less electron-deficient
olefins. Aldehydes were generally restricted to specific class to
avoid the decarbonylation problem and to enable the
desirable acyl radical addition of olefins to take place.
Furthermore, for an intermolecular hydroacylation approach,
the installation of a functional group instead of a hydrogen
atom through trapping of the acylative intermediate remains a
largely elusive problem. We envisioned that the rationally
designed strategy could provide a promising solution to these
synthetic problems. Herein, we present our findings on the
establishment and application of this strategy in the
development of a chemoselective acylazidation of olefins.
time
h)
epoxide
b
(%)
yield
entry
1
cat.
solvent
b
(
(
3a %)
n.r.
n.r.
−
−
CH
3
CN
12
12
<1
6
n.r.
n.r.
30
c
2
C1
C1
C1
C1
C1
C1
C1
C1
C2
C3
C4
C5
C6
C1
C1
C1
C1
C1
CH CN
3
d
3
3
CH CN
4
5
6
7
CH CN
3
< 5
6
57
45
27
39
52
75
65
68
11
65
55
58
54
49
51
−
EtOAc
DCM
6
6
< 5
< 5
< 5
< 5
< 5
< 5
7
toluene
6
e
8
H O/CH CN
2 3
3
9
H2O/EtOAc
3
1
1
1
1
1
1
0
1
2
3
4
5
H
H
H
H
H
H
2
2
2
2
2
2
O/EtOAc
O/EtOAc
O/EtOAc
O/EtOAc
O/EtOAc
O/EtOAc
3
3
Results and discussion
5
Extensive investigation on numerous possible combinations of
competitive reactants was carried out. Encouragingly, we were
able to identify that the addition of a combination of aldehyde
and sodium azide to the (salen)Mn(III) catalysis system could
suppress oxygenation approaches, resulting in the
chemoselective formation of an acylazidation product. Organic
azides can participate in a range of important reactions
9
< 5
< 5
< 5
< 5
< 5
< 5
41
5
f
6
g
16
H2O/EtOAc
6
h
17
H2O/EtOAc
6
i
8
1
1
H
2
O/EtOAc
6
2
9
30
including Staudinger ligation , 1,3-dipolar cycloaddition , and
the aza-Wittig reaction , making them highly attractive
d
9
H2O/EtOAc
4
3
1
a
3
2
targets for organic synthesis . A range of elegant methods
Unless otherwise noted, all the reactions were carried out
with 1a (0.3 mmol), 2a (1.5 mmol), NaN (1.2 mmol), PhIO (0.9
3
have been developed for azidation of olefins and C-H
3
3
3
azidation . To optimize the reaction condition, styrene was
4
mmol) and
C (2 mol%) in 3.0 mL solvent as indicated at room
d
b
c
used as a model substrate while n-butylaldehyde and sodium temperature. Isolated yield. Without PhIO. Without 2a and
e
azide were employed as a combination of competitors. As NaN
3 2
. 6.4 mL mixed solvent was used (H O/organic solvent =
f
shown in Table 1, initially, several control experiments were 1/0.6, entries 8-19). 1 mol%
g
was used. 0.9 mmol 2a was
C
h
i
conducted. No product was observed in the absence of either used. 2.0 equiv PhIO was used. 4.0 equiv PhIO was used. n.r.
salen)Mn(III) catalyst or PhIO (entries 1-2). In the absence of
n-butylaldehyde and sodium azide, as previously reported by
(
=
no reaction.
1
2
Kochi and co-workers , a fast consumption of styrene was
observed (<1 h, >95% conv. of styrene, 30% epoxide, entry 3).
Acylazidation product was formed in 57% yield catalyzed by C1
epoxide was obtained in the absence of n-butylaldehyde and
sodium azide (entry 19).
The substrate scope was investigated next. As shown in
Scheme 1, remarkably, all the representative aldehydes, such
as linear-, branched-aliphatic aldehydes and aromatic
aldehyde, could be tolerated and the desired products were
obtained in reasonable yields (3a−d). Aromatic rings of olefins
bearing electron-donating or electron-withdrawing groups
were tolerated. Meanwhile, substituent groups could be
incorporated in diversified positions, delivering ortho-, meta-,
and para-substituted products. Furthermore, multi-substituted
aromatic rings were amendable to this transformation (3m−o).
The employment of several α-substituted styrene derivatives
for the synthesis of a range of tertiary azides was successful
in CH
solvent of EtOAc and H
3
CN (entry 4). Solvent optimization showed that a mixed
O is an optimal choice, which afforded
2
the desired product in 75% yield (entries 5-9). The evaluation
of different (salen)Mn(III) complexes revealed that catalyst C1
is a promising candidate (entries 10-14). Upon using 1 mol% of
catalyst C1, the reaction yield was decreased (entry 15).
Further optimization of the amount of aldehyde and
iodosobenzene did not improve the reaction yield (entries 16-
18). The optimized reaction condition did not provide an
observable quantity of epoxidation product. In contrast, 41%
2
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b
at room temperature.
The diastereoselectivity was
1
determined by H NMR analysis of the crude reaction mixture
c
and yields refer to the isolated major product. 1 mol% catalyst
d
C1 and 6.0 equiv. PhIO was used (compound 3t). The
diastereoselectivities of 4b, 5a and 5b refer to the ratio of the
two major isomers.
(
3p−s). Both trans- and cis-stilbene could be used as substrates
to afford the same product with similar diastereoselectivity in
0% and 54% yield, respectively (3t). Under standard condition
5
using cis-stilbene as substrate, acylazidation product 3t was
obtained in 30% yield along with 17% epoxide. Interestingly,
reducing catalyst loading to 1 mol% was effective for a
vigorous competition between the reactions of acylazidation
and epoxidation of stilbene since the acylazidation approach
overwhelmingly dominated the reaction pathways.
heterocyclic substrate could also be tolerated in this reaction
3u).
Next, using electron-deficient α, β-unsaturated amides as
A
(
substrates was studied. All the α, β-unsaturated amides
smoothly afforded the desired products with moderate to
good diastereoselectivity in reasonable yields (Scheme 1).
Aromatic groups with different electrical properties such as
electron-withdrawing or electron-donating groups were
tolerated, as were ortho-, meta-, and para- substituted
aromatic rings. The structure of 3aa was confirmed by single-
3
0
crystal X-ray diffraction . This methodology could be applied
to more complex contexts. Estrone derivatives could be
applied in this transformation. It is of significance to
incorporate azido group into peptide derivatives which can be
applied to the synthesis of a wide range of complex molecules
3
1-32
with promising biological activities
provides concise pathway for the preparation of
. This methodology
a
azidopeptide derivatives (Scheme 1).
As shown in Figure 2, a series of control experiments were
carried out to probe the mechanism (see Supporting
Information). Considering the significant work established by
Jacobsen and co-workers that azide ring-opening of epoxides
3
3-34
can be efficiently catalyzed by metal-salen complexes
, the
replacement of styrene with styrene oxide did not generate
product 3a either under standard reaction condition or
without PhIO. This experiment can exclude the possibility that
3
a was generated from complex transformation of styrene
oxide. Furthermore, established work revealed that α, β-
unsaturated ketones could be generated through copper-
3
5
catalyzed oxidative coupling of alkenes with aldehydes
.
Meanwhile, Jacobsen and co-workers discovered that Lewis
acid was able to catalyze conjugate addition of azide to α, β-
3
6-37
unsaturated ketones
. However, α, β-unsaturated ketone
((E)-1-phenylhex-1-en-3-one) was not observed under
standard reaction condition using 1a and 2a as starting
materials. The reaction between a synthetic α, β-unsaturated
ketone ((E)-1-phenylhex-1-en-3-one) and sodium azide
catalyzed by (salen)Mn(III) C1 with (or without) PhIO failed to
deliver the conjugate product 3a, which excludes a possible
Lewis acid-catalyzed conjugate addition pathway.
a,b
Scheme 1 Substrate Scope . Unless otherwise noted, all the
reactions were carried out with 1a (0.3 mmol), 2a (1.5 mmol),
3 2
NaN (1.2 mmol) and C (2 mol%) in 6.4 mL H O/EtOAc (1/0.6)
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a more stable dibenzylic radical. All these results clearly point
out to an acyl radical addition pathway.
A: The generation of acyl radical
EtO2C
N
N
CO2Et
EtO2C
O
O
N
NH
CO2Et
To probe the azidation process, several control
experiments were carried out. Nearly the same moderate
enantioselectivity of 3d was obtained in the presence of 2
mol% and 10 mol% Jacobsen’s catalyst C7 while no product
was observed without this catalyst. However, an
intramolecular reaction using 2-(allyloxy)benzaldehyde as
substrate could proceed in the absence of a catalyst to afford
C1 (2 mol%), PhIO (3.0 equiv.)
EtOAc/H2O, rt, N2
n-PrCHO
n-Pr
10 min, 95%
n-Pr
6
B: Acylation
(1) radical clock experiments:
O
N3
O
n-Pr
C1 (1 mol%), PhIO (5.0 equiv)
Ph
Ph
+
n-PrCHO + NaN3
N3
Me
Ph
n-Pr
Me
EtOAc/H2O, rt, N2
1
2a
3v
1v
3v'
not observed
1% (major:minor = 2.2:1)
4
1
chroman derivatives . Considering the potential pathway that
the oxidation of radical intermediate by manganese would
lead to the formation of carbocation, then 20 equiv methanol
was added to the standard reaction system to competitively
trap the carbocation. However, neither methoxylated product
Ph
N3
Ph
OMe
O
MeO
N3
Ph
O
C1 (2 mol%), PhIO (6.0 equiv)
+
PhCHO + NaN3
Ph
Ph
2a
EtOAc/H2O, rt, N2
OMe
3w
Me
3w' Me
1w
12% (major:minor = 1.4:1)
not observed
(2) competitive acyl addition with the use of different olefins:
C1 (2 mol%)
PhIO (1.0 equiv relative to 1p+1a)
N3
O
N3
O
7
nor hydroxylated product
product of competitive Ritter reaction was not detected upon
using CH CN/H O as solvent. Furthermore, the competition
between two radical rebound approaches was observed and a
considerable amount of hydroxylated product (30%) was
isolated in dry CH CN. This experiment suggests the formation
8 was observed. Furthermore,
Ph
Ph
+
n-Pr Ph
+
+ n-PrCHO
+
NaN3
Ph
n-Pr
Ph
EtOAc/H2O, rt, N2
Ph 3p
3a
3a: 8%
1
p
1a
p : 1a = 1 : 1
2a
(
2 h, isolated yield) 3p: 46%
1
3
2
3
p:3a = 10.0:1 (20 min, 1H NMR ratio)
9
C: Azidation
1) the role of (salen)Mn(III):
(
3
of an acyl radical and a hydroxomanganese(IV) intermediate
originated from (O=)C-H abstraction by the reactive
t-Bu oxomanganese(V) species. These experiments indicate a azido-
C7 (x mol%), PhIO (3.0 equiv)
N3
O
Ph
+
RCHO + NaN3
1a
EtOAc/H2O, rt, N2
N
O
N
O
Ph
R
Mn
3
a: R = n-Pr, C7 (2 mol%), 65%, er: 71:29
t-Bu
Cl
C7 (0 mol%), 0%;
rebound pathway. Only 4% of
9 was isolated which indicates
t-Bu
t-Bu
3
d: R = Ph,
C7 (2 mol%), 52%, er: 75:25;
C7 (10 mol%), 31%, er: 74:26.
C7
the rate of azido-rebound is much faster than hydroxy-
rebound under standard reaction condition. Furthermore, in
optically pure
(
2) in the presence of other nucleophiles:
N3
O
OR
O
3
the absent of NaN , product 9 was isolated in 41% yield, which
C1 (2 mol%), PhIO (3.0 equiv)
1
a + 2a
Ph
n-Pr
Ph
Ph
n-Pr
clearly revealed that both the generation of the acyl radical
and subsequent radical addition of olefin can occur in the
NaN3, EtOAc/H2O/MeOH, rt, N2
trace
3
a
60%
7
: R = Me; 8: R = H
N3
O
AcHN
Ph
O
C1 (2 mol%), PhIO (3.0 equiv)
absence of NaN
3
. Further control experiments revealed that
1a + 2a
n-Pr
n-Pr
52%
NaN3, CH3CN/H2O, rt, N2
3a
not observed
Ritter product
the acylazidation product 3p is not generated from
transformation of hydroxylated compound 9.
(3) the observation of the competition between two radical rebound approaches:
N3
O
OH O
C1 (2 mol%), PhIO (3.0 equiv.)
o
+
Ph
Ph
CH3CN, rt, 4A MS, 5 h, N2
Ph
Ph 3p
n-Pr
Ph
Ph
n-Pr
Mn
R'
R'
+
n-PrCHO
+
NaN3
9
44%
p (77%)
30%
X
standard condition
1p
2a
3
+
9 (4%)
NaN3
N3
O
(4) acyl addition without NaN3:
R1
R
PhIO
R2
Mn
standard condition
8 h
NaN3, standard condition (or without PhIO)
R'
R'
9
(41%)
isolated
3p
4
N3
1
p + 2a
O
standard condition
8 h
NaN3
(salen)Mn
3p
4
radical rebound
M1
oxidation
R2
R1
L
shutting
down
O
Figure 2 Probing mechanism.
Mn
N3
R'
R'
Mn
R1
R'
O
R'
H
O
H
O
+
H
N3 M2
R1
R1
R
H
R2
The generation of acyl radical in the presence of Mn(III)
and PhIO was observed by using diethyl azodicarboxylate as a
H
R2
H
R2
MnLn
R1
R
R
R
C-H abstraction
3
8
M4
O
trapping agent . Furthermore, using a radical clock substrate
afforded the ring-opening product 3v. Newcomb-type
cyclopropane substrate 1w was employed to differentiate
R2
radical addition
epoxidation
OH
1v
R1
L
OH
H
R2
3
9-40
Mn
Mn
R
R1
R'
R'
R'
R'
between a radical approach and a cationic pathway
. Acyl
R2
O
N3
N3
M3
addition to the olefin 1w occurs with subsequent cleavage of
radical rebound
M3'
L = OH or N3
O
R
NaN3
the benzylic cyclopropyl bond rather than α-methoxy
cyclopropyl bond. Furthermore, an intermolecular competitive Figure 3 Plausible mechanism.
reaction between substrates 1p and 1a was carried out.
Despite more steric hindrance, compound 3p was obtained as
a major product and a ratio of 10:1 (20 min, 3p
3a) was was depicted in Figure 3. Initially, a ligand exchange process
observed upon using 1:1 mixture of 1p and 1a
This resulted in manganase-bound azide M1 The resting
observation can be attributed to the competitive generation of (salen)Mn(III) is oxidized by PhIO, generating a reactive
Based on these obtained results, a possible mechanism
:
.
a
.
4
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oxomanganese(V) intermediate M2. The oxomanganese(V)
species is capable of selectively abstracting a hydrogen from
aldehyde to form intermediate M3 and an acyl radical. The
subsequent acyl radical addition of a manganese-activated
alkene would generate a pending radical intermediate. Finally,
Biochemistry, 3rd ed., Ed. P. R. Ortiz de Montellano, Plenum
Press, New York, 2005.
1
1
2 K. Srinivasan, P. Michaud and J. K. Kochi, J. Am. Chem. Soc.,
986, 108, 2309−2320.
3 J. T. Groves, W. J. Kruper and R. C. Haushalter, J. Am. Chem.
Soc., 1980, 102, 6375 6377.
1
−
azido-rebound via complex M4 releases the final product and 14 Y.-R. Luo, Comprehensive Handbook of Chemical Bond
Energies, CRC, Boca Raton, 2007.
(
salen)Mn(III) catalyst.
1
5 C. Chatgilialoglu, D. Crich, M. Komatsu, and L. Ryu, Chem.
Rev., 1999, 99, 1991˗2070.
6 M. C. Willis, Chem. Rev., 2010, 110, 725–748.
1
1
1
Conclusions
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induce an intermolecular acylazidation of olefins using
aldehydes and sodium azide as competitive reactants. Both
carbonyl and azido groups were incorporated into simple
olefinic compounds as well as complex targets. This
transformation enables electron-deficient, neutral and even
electron-rich alkenes to participate in an acyl radical addition
process at room temperature. The representative aldehydes,
such as linear-, branched-aliphatic aldehydes and aromatic
aldehyde, could be used as effective reactants. Potentially, the
strategy described herein could open the doors to new
catalytic reactivity that has been unexplored.
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Conflicts of interest
There are no conflicts to declare.
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We gratefully acknowledge the National Natural Science
Foundation of China (21772113, 21302075, 11501454), The
Key Research and Development Plan of Shandong Province
(2017GGX70109), The Fundamental Research Funds of
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