Iron-catalyzed peroxidation-carbamoylation of alkenes with hydroperoxides and formamides: Via formyl C(sp2)-H functionalization

Article abstract of DOI:10.1039/c7cc08074c

A reaction protocol in which FeCl₃ and tert-butyl hydroperoxide facilitated a selective radical coupling reaction of aryl alkenes or 1,3-enynes with tert-butyl hydroperoxide and formamides to prepare an array of β-peroxy amides has been achieved. The β-peroxy amide could serve as a synthetic precursor which was facilely converted to β-hydroxy amide, β-keto amide and β-lactam following subsequent chemical transformation.

Full text of DOI:10.1039/c7cc08074c

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Iron-Catalyzed Peroxidation-Carbamoylation of Alkenes with
Hydroperoxides and Formamides via Formyl C(sp2)-H
Functionalization
Received 00th January 20xx,
Accepted 00th January 20xx
Jun-Kee Cheng,‡b Liang Shen,‡b Liu-Hai Wu,b Xu-Hong Hu*a and Teck-Peng Loh*ab
DOI: 10.1039/x0xx00000x
www.rsc.org/
A reaction protocol in which FeCl3 and tert-butyl hydroperoxide envisioned to devise alternative access to yield broadly useful
facilitated selective radical coupling reaction of aryl alkenes or 1,3- β-hydroxy amides by an Fe(III)-catalyzed carbamoylation of
enynes with tert-butyl hydroperoxide and formamides to prepare alkenes using DMF (or its variants) under relatively neutral
an array of β-peroxy amides has been achieved. The β-peroxy conditions, which serves as an attractive complementary
amide could serve as synthetic precursor which was facilely protocol to existing methods for the synthesis of β-hydroxy
converted to β-hydroxy amide, β-keto amide and β–lactam amides, rerouting from the conventional aldol pathway.
following subsequent chemical transformation.
By virtue of atom economy, direct functionalization of the
formyl C(sp2)-H bond10 in C-C bond formation has been widely
demonstrated in aryl halides,11 heteroarenes,12 aryl
isonitriles,13 and carboxylic acids.14 Precedent reactions of
formamides with simple alkenes using ruthenium,15
palladium16 or nickel17 catalysts, appeared as facile approach
solely to the hydroamidation products. Independently, Li and
co-workers have reported the assembly of α,β-unsaturated
amides from an oxidative radical pathway.18 Herein, we wish
to report an efficient method to perform peroxidation-
carbamoylation of 1,3-enynes and arylalkenes using different
formamide derivatives through selective formyl C(sp2)-H
functionalization.
Alkene difunctionalization presents a rapid and efficient single-
step method to construct molecular complexity.1 Significant
advancement has been made in transition metal-catalyzed
2
3
4
dioxygenation
，
diamination
，
and aminooxygenation
which features concomitant introduction of two heteroatom
functionalities across the double bond. The relatively limited
reports on carbooxygenation reaction are complemented by
the radical-mediated strategy which is made viably by the high
reactivity of carbon-centered radicals towards unsaturated
chemical systems.5,6
In the context of three-component alkene radical
carbooxygenation, aryl radicals,7 alkyl radicals8 as well as
carbonyl radicals9 could be generated in-situ from the
activated precursors or via direct C-H functionalization and
undergo subsequent addition to alkene. Taniguchi et al.
accomplished alkene radical oxycarbonylation on wide scope
of terminal alkenes with molecular oxygen and respective
carbazate precursors.9b Li’s group, on the other hand,
established the three-component oxycarbonylation reaction of
conjugated alkenes with aldehydes and hydroperoxide as the
oxygen source.9c-e
In continuation of our interest to attain the synthesis of
peroxy compounds via alkene difunctionalization,8m,n we
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: ias_xhhu@njtech.edu.cn
b.Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences, Nanyang Technological University, Singapore 637371,
Singapore. E-mail: teckpeng@ntu.edu.sg
Scheme 1 Transition-metal-catalyzed radical carbooxygenation of
alkene/enyne.
The investigation was commenced by treating styrene with
4 equiv of TBHP in neat DMF in the presence of 10 mol% of
FeCl2 (Table 1, entry 1). We were delighted to obtain 57% of
the hypothesized product after 5 h. Among other metal salts
† Electronic Supplementary Information (ESI) available: Detailed experimental
procedures, and analytical
DOI: 10.1039/x0xx00000x
‡ These two authors contributed equally.
data
for all
new compounds. See
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Table 2 Reaction scope of styrene (1a) with formamidesa,b
tested under similar condition (Table 1, entries 2-9), FeCl3
exhibited best catalytic activity to afford 61% yield of peroxy-
carbamoylated product while other metal salts showed
inferior effectiveness for this reaction. The isolated yield could
be slightly augmented to 63% when 20 mol% of benzoic acid
was added as additive and other acidic additives could not
further enhance the reaction (Table 1, entries 11-15). The
reaction did not work to yield any desired product in the
absence of metal catalyst (Table 1, entries 10 and 12).
Increasing the amount of TBHP and performing reaction under
inert atmosphere were futile to generate the desired product
in higher chemical yield (Table 1, entries 16-17).
a Unless otherwise noted, reaction conditions: 1a (0.50 mmol), 2 (2.0 mmol),
3 (1.6 mL), FeCl3 (0.05 mmol), PhCO2H (0.10 mmol), 65 °C, air. c No PhCO2H. b
Table 1 Optimization of reaction conditionsa
d
e
Isolated yield.
3 (6.0 mmol), DMSO (1.6 mL). The d.r. value was
approximated as 1:1.
Table 3 Reaction scope of arylalkenes with N-ethylformamide (3b)a,b
entry catalyst
additive
yieldb (%)
57
61
46
42
10
<5
<5
16
40
-
1
2
3
4
5
6
FeCl2
FeCl3
FeBr3
Fe(TFA)3
Fe(OTf)2
CuCl
-
-
-
-
-
-
-
-
7
8
9
CuCl2
Co(OAc)2
Co(acac)3
-
FeCl3
-
FeCl3
FeCl3
FeCl3
FeCl3
FeCl3
-
-
10
11
12
13
14
15
16c
17d
PhCO2H
PhCO2H
4-NO2C6H4CO2H
2,4-(MeO)2C6H3CO2H
tBuCO2H
63
-
a Reaction conditions: 1 (0.50 mmol), 2 (2.0 mmol,), 3b (1.6 mL), FeCl3 (0.05
mmol), PhCO2H (0.10 mmol), 65 °C, 2-3.5 h, air. b Isolated yield.
37
57
52
52
57
To further expand the substrate scope for this functionalization
reaction, 1,3-enynes were tested for this transformation using DMF
as the standard coupling partner (Table 4). Among the tested
additives, whether Lewis acid (Zn(OTf)2, AlCl3 and InCl3), base
(LiOAc, K2CO3, HNEt2 and DBU), or other carboxylic acids, benzoic
acid showed the highest reactivity (Table S1, ESI†). The absence of
benzoic acid led to a significant decrease of the reaction yields for
some enyne substrates. Delightedly, it was observed to
demonstrate good substituent compatibility to accommodate 1,3-
enynes bearing different silyl groups, phenyl substituents as well as
aliphatic alkyl groups. Aryl enynes carrying halogen and alkyl
functionalities underwent this transformation to afford 7a-e in
moderate yields, which would render these compounds amenable
for post-functionalization. Enynes tethered with common silyl
protecting moieties furnished the respective products 7f-7h in 52-
61% isolated yields. Additionally, the desired peroxidation-
carbamoylation products 7i-7j could also be prepared in moderate
yields when aliphatic enynes were subjected under the same
reaction conditions. 1,3-Butadiene was found to be an effective
substrate with our protocol to give the regioisomeric 7k and 7k’ in
total yield of 48%.
PhCO2H
PhCO2H
a
Reaction conditions: 1a (0.50 mmol), 2 (2.0 mmol), 3a (1.6 mL),
catalyst (0.05 mmol), 65 °C, 5 h, air. b Isolated yield. c 2 (2.5 mmol).
Under N2 atmosphere.
d
We began to probe the reaction generality by examining the
reaction of styrene with different formamides under the optimized
reaction conditions (Table 2).19 Aside from DMF, reaction with N,N-
diethylformamide successfully gave 4b in good yield. Cyclic
formamides could also be smoothly assembled onto the styrene to
give 47% yield of 4c and 4d, respectively. All N-monosubstituted-
formamides tested could be well suited to afford the β-peroxy
amides 4e-4g in moderate to good yields which bear an ethyl,
phenyl and cyclohexyl group. Delightfully, N-formyl amino acid
esters also appeared to be compatible substrates to furnish 4h and
4i in moderate yields.
Several styrene derivatives were then explored employing N-
ethylformamide (3b) as standard coupling partner and all were
found to be suitable substrates for this reaction protocol (Table 3).
Regardless of substitution pattern, styrenes with diversified
functional motifs such as methoxy, bromo, acetoxy, trifluoromethyl,
together with the sterically demanding tert-butyl group delivered
the corresponding products 5a-5e in synthetically useful yields of
59-77%, indicating that electronic effect is not critical for this
transformation. Vinylnaphthalene led to the formation of 5f in a
slightly lower yield of 56% whilst α-methylstyrene could also result
in the preparation of tertiary peroxides 5g in 64% yield.
Similarly, reaction of phenyl enyne with other formamide
derivatives also led to the corresponding β-peroxy amides facilely.
Reaction with DMF produced 7a in 51% yield while increasing chain
length depressed the product yield of 7l to 32%. Cyclic formamides
derived from morpholine and piperidine could also be smoothly
assembled onto the enyne to give 34% yield of 7m and 44% yield of
7n, respectively. N-Monosubstituted-formamides afforded the β-
peroxy amides 7o-7r in moderate yields.
2 | J. Name., 2012, 00, 1-3
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Table 4 Reaction scope of 1,3-enynes and 1,3-diene with formamidesa,b
Scheme 3 Proposed mechanism.
In summary, we have established a three-component
radical coupling reaction which assembled β-peroxy amides
with hydroperoxide and formamide derivatives through
difunctionalization of 1,3-diene, 1,3-enynes as well as styrenes
carrying varied functional groups under mild conditions. This
strategy complements the conventional aldol reaction to
synthesize β-hydroxy carbonyl compound, wherein the basic
condition could lead to the undesired homo-condensation and
dehydration products. In addition, the resulting β-peroxy
amides serve as versatile synthetic precursor for β-hydroxy
amide, β-keto amide and β–lactam. Further synthetic
application of this reaction protocol is underway in our
laboratory.
a Unless otherwise noted, reaction conditions: 6 (0.30 mmol), 2 (1.2 mmol),
b
3 (1.0 mL), FeCl3 (0.03 mmol), PhCO2H (0.06 mmol), 65 °C, 1.25 h, air.
Isolated yields. c No PhCO2H. d Performed on 0.50 mmol scale, ratio of 7k:7k΄
was 1:2.4. e 3 (3.6 mmol), DMSO (1.0 mL).
Financial support was provided by the NNSFC (21432009),
the Natural Science Foundation of Jiangsu Province, China
(BK20170967), the SICAM Fellowship by Jiangsu National
Synergetic Innovation Center for Advanced Materials, the
Singapore Ministry of Education Academic Research Fund
[MOE2014-T1-001-102, MOE2015-T1-001-070], and Singapore
National Research Foundation (NRF2015NRF-POC001-024).
Conflicts of interest
There are no conflicts to declare.
Scheme 2 Synthetic transformation on 7a and 7p.
Notes and references
Subsequent chemical transformations were attempted on β-
peroxy amide 7a (Scheme 2). Kornblum-DelaMare rearrangement
took place when subjected under basic condition to afford the
corresponding β-keto amide 8,20 while reduction of the peroxy
group with zinc under acidic condition gave β-hydroxy amide 9 in
79% yield.21 It is noteworthy that N-phenyl-β-peroxyamide
prepared using our reaction protocol could serve as alternative
synthetic precursor for the β-lactam ring 11.22
In accordance with the precedent reports and current
experimental observation, a plausible mechanism was devised in
Scheme 3.13a,23 Iron catalyst was thought to firstly mediate the
formation of tert-butoxy and tert-butylperoxy radicals. The former
abstracted the formyl C-H bond of formamide homolytically,
revealing the aminoacyl radical which then added to the double
bond. The propargylic/benzylic radical intermediate coupled with
the tert-butylperoxyl radical in a selective fashion to give the
desired product, which could be elucidated by the persistent radical
effect.24 The addition of benzoic acid was found to promote
noticeable enhancement of the reaction yields of some substrates,
though its exact role remains elusive at this stage.25
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Table of Contents
A three-component radical coupling reaction of aryl alkenes or 1,3-enynes with tert-butyl
hydroperoxide and formamides for the efficient synthesis of β-peroxy amides.