Visible-Light-Driven Palladium-Catalyzed Oxy-Alkylation of 2-(1-Arylvinyl)anilines by Unactivated Alkyl Bromides and CO2: Multicomponent Reactions toward 1,4-Dihydro-2 H-3,1-benzoxazin-2-ones

Article abstract of DOI:10.1021/acs.orglett.9b02700

A visible-light-driven palladium-catalyzed radical oxy-alkylation of 2-(1-arylvinyl)anilines with unactivated alkyl bromides and CO₂ has been developed toward 1,4-dihydro-2H-3,1-benzoxazin-2-ones. This multicomponent reaction (MCR) starts with

Full text of DOI:10.1021/acs.orglett.9b02700

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Visible-Light-Driven Palladium-Catalyzed Oxy-Alkylation of 2‑(1-
Arylvinyl)anilines by Unactivated Alkyl Bromides and CO :
2
Multicomponent Reactions toward 1,4-Dihydro‑2H‑3,1-benzoxazin-
2-ones
Song Sun, Cong Zhou, Jin-Tao Yu, and Jiang Cheng*
School of Petrochemical Engineering, and Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, Changzhou
University, Changzhou 213164, P. R. China
*
S Supporting Information
ABSTRACT: A visible-light-driven palladium-catalyzed radical oxy-alkylation of 2-(1-arylvinyl)anilines with unactivated alkyl
bromides and CO has been developed toward 1,4-dihydro-2H-3,1-benzoxazin-2-ones. This multicomponent reaction (MCR)
2
starts with (1) carboxylation of an amino by CO ; (2) formation of Pd(I) and an alkyl radical via visible-light-driven reaction of
2
alkyl bromides and Pd(0); (3) addition of an alkyl radical to the vinyl followed by single electron transfer (SET) oxidation to
the carbocation by Pd(I); and (4) cyclization via intramolecular nucleophilic attack of the carboxylate anion to carbocation.
he utilization of CO as a one-carbon source toward
value-added chemicals, especially heterocyclic com-
cyclization reaction of 2-vinylaniline derivatives with 1,3-
dichloro-5,5-dimethylhydantoin (Scheme 1b). Nevertheless,
2
13
T
pounds, has received considerable attention in recent
to date, the sustainable procedure on the fixation of CO to
2
1
,2
14
years. Among which, the carboxylative cyclizations triggered
access such frameworks has been rarely studied. As part of
15
by the reactions of CO2 with N-nucleophile, such as
our continuing studies on the chemical conversion of CO ,
2
3
4
5
allylamines, propargylamines, and o-alkynylanilines, are
extremely fascinating, affording useful nitrogen-containing
heterocycles with potentially diverse bioactivities. Undoubt-
edly, the development of such reactions proceeding with either
new substrates or new strategies on known substrates would
we herein present a novel procedure toward 1,4-dihydro-2H-
3,1-benzoxazin-2-ones, proceeding with a three-component
reaction of 2-(1-arylvinyl)anilines, alkyl bromides, and CO
2
promoted by a photoredox and palladium dual-catalysis system
at room temperature (Scheme 1c).
Initially, we tested the reaction of 2-(1-phenylvinyl)aniline
1a (0.2 mmol), 1-bromoadamantane 2o (0.3 mmol), and
atmospheric pressure CO to optimize the reaction conditions.
2
dramatically enlarge the applicable scope of CO fixation,
2
leading to new value-added products with complexity and
diversity. With the development of visible-light-driven
6
,7
First, during the screening of photocatalysts, only Pd(PPh3)4
reactions, we have witnessed many elegant examples on
visible-light-promoted carboxylative cyclization of allylamines
(
5 mol %) was efficient under the irradiation of 2 × 3 W blue
LEDs in the presence of Cs CO (3 equiv) as the base, leading
with bromides and CO . For instance, He developed the
2
3
2
to the annulation product 3a in 45% yield (Table 1 entries 1−
radical-initiated carboxylative cyclization leading to fluorine
containing 2-oxazolidinones whereby the sequential radical
addition, carboxylation, SET oxidation, and intramolecular
t
3
). Among the tested bases such as KO Bu (<5%), DBU
(
(
58%), TBD (85%), and MTBD (61%), TBD was the best
Table 1, entries 3−7). Notably, the solvent also had a
8
cyclization occurred. Afterward, Yu described a simila9r
profound effect on the reaction efficiency, and DMSO (85%)
procedure toward highly functionalized 2-oxazolidinones.
was superior to DMF (78%) and MeCN (36%, Table 1, entries
However, compared with allylamines, the fixation of CO by
2
7
−9). Pd(PPh ) Cl gave a comparable yield (75%). However,
o-alkenylanilines through a similar procedure has never been
3 2
2
1
0
Pd(OAc) (<5%) and Pd (dba) (<5%) almost inhibited the
investigated before.
2
2
3
reaction (Table 1, entries 7, and 10−12). Additionally, 5 mol
Meanwhile, 1,4-dihydro-2H-3,1-benzoxazin-2-ones are im-
%
of Pd(PPh ) and 1.5 equiv of 1-bromoadamantane were
portant structural motifs that widely exist in biologically active
3 4
11
natural products and medicines (Scheme 1). Traditional
synthetic methods included the cyclization of (2-aminoaryl)-
Received: August 1, 2019
12a,b
methanols with phosgene or CBr (Scheme 1a),
and halo-
4
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b02700
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 1. Representative 1,4-Dihydro-2H-3,1-benzoxazin-
in the absence of each reaction parameter (Table 1, entries
14−15).
Having established the optimized reaction conditions, first,
the scope and limitation of alkyl bromides were investigated, as
summarized in Figure 1. Generally, the catalytic system
2
-ones and Synthetic Pathways
Table 1. Selected Results for Screening the Optimized
a
Reaction Conditions
b
entry
catalyst
base
solvent
yield (%)
c
1
fac-Ir(ppy)3
Cs CO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
MeCN
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
N.R.
Figure 1. Scope of Alkyl Bromides. Reaction conditions: 2-(1-
phenylvinyl)aniline 1a (0.2 mmol), alkyl bromide 2 (0.3 mmol),
2
3
3
3
c
2
Ru(bpy) Cl ·6H O
Cs CO
N.R.
45
<5
58
61
85
78
36
75
<5
3
2
2
2
Pd(PPh ) (0.01 mmol, 5 mol %), and TBD (0.6 mmol) in DMSO
3
4
5
6
7
8
9
Pd(PPh3)4
Pd(PPh3)4
Cs CO
3 4
2
t
(2.0 mL) were irradiated with 2 × 3 W blue LEDs for 24 h in a sealed
KO Bu
a
Schlenk tube at room temperature, unless otherwise noted. Deter-
Pd(PPh3)
4
DBU
1
b
mined by H NMR. 2-(1-Phenylvinyl)aniline 1a (1.0 mmol), 1-
bromoadamantane 2o (2.0 mmol), Pd(PPh ) (0.1 mmol, 10 mol %),
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
MTBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
TBD
−
3
4
and TBD (3.0 mmol) in DMSO (10.0 mL) were irradiated with 2 × 3
W blue LEDs for 24 h in a 25 mL Schlenk tube with a CO balloon at
2
Pd(PPh3)
4
room temperature.
10
11
12
13
14
15
Pd(PPh ) Cl
3 2 2
Pd(OAc)2
exhibited a broad substrate scope and high functional group
tolerance. Importantly, primary (40−78%, 3a−f), secondary
(61−88%, 3g−n), and tertiary alkyl bromides (85%, 3o) all ran
smoothly under the optimized conditions. Particularly, ethyl 5-
bromopentanoate provided 3d in 51% yield. Both acyclic
(72%, 3e) and cyclic (78%, 3f) acetal worked well under the
procedure. Notably, the cyclic secondary alkyl bromides, such
as 2-bromoadamantane (72%, 3g), bromocyclopropane (62%,
Pd (dba)3
<5
2
d
e
f
Pd(PPh3)
4
75 , 81 , 83
N.R.
g
Pd(PPh3)4
Pd(PPh3)4
N.R.
a
Reaction conditions: 2-(1-phenylvinyl)aniline 1a (0.2 mmol), 1-
bromoadamantane 2o (0.3 mmol), catalyst (0.01 mmol, 5 mol %),
base (0.6 mmol), solvent (0.1 M), 2 × 3 W blue LEDs, 24 h, in a
sealed Schlenk tube under room temperature, unless otherwise noted.
Isolated yield. Catalyst (0.002 mmol, 2 mol %). Pd(PPh ) (2.5
mol %). Pd(PPh ) (10 mol %). 1-Bromoadamantane (0.4 mmol).
Without Pd(PPh ) or in dark. Ad = adamantan-1-yl. DBU = 1,8-
diazabicyclo[5.4.0]undec-7-ene. TBD = (1,5,7-triazabicyclo[4.4.0]-
dec-5-ene). MTBD = 1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido-
1,2-a]pyrimidine. N.R. = no reaction.
3
h), bromocyclobutane (88%, 3i), bromocyclohexane (70%,
b
c
d
3
4
e
f
3j), 4-bromo N-Boc piperidine (61%, 3k), and 4-bromotetra-
hydro-2H-pyran (78%, 3l), all served as good reaction
partners. The product 3n was isolated in 71% yield (dr = 1/
3
4
g
3
4
1
). To our delight, ester (51%, 3d), acetal (72%−78%, 3e−3f),
[
N-Boc (61%, 3k), and ether (78%, 3l) groups, which were
handles for potential further functionalization, survived well in
this procedure. Additionally, a 1 mmol scale reaction of 1a with
2
o also ran smoothly under slightly modified conditions to
sufficient enough for high reaction efficiency (Table 1, entry
3). During the blank experiments, the reaction failed to work
afford 3o in 73% yield. The structure of 3b was further
confirmed by X-ray crystallography study (CCDC 1920540).
1
B
DOI: 10.1021/acs.orglett.9b02700
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Subsequently, the substrates scope of 2-(1-arylvinyl)anilines
was also investigated as shown in Figure 2. As expected, the
Scheme 2. Preliminary Mechanism Study
2
b). This result further confirmed the involvement of a radical
pathway during the procedure.
On the basis of the aforementioned results and some relative
previous studies, a tentative mechanism is outlined in Scheme
6g−l,9,16
3
.
First, the excited state Pd(PPh ) A is formed under
3 4
Scheme 3. Proposed Mechanism
Figure 2. Scope of 2-(1-Arylvinyl)anilines. Reaction conditions: 2-(1-
arylvinyl)aniline 1 (0.2 mmol), bromocyclobutane 2i (0.3 mmol),
Pd(PPh ) (0.01 mmol, 5 mol %), and TBD (0.6 mmol) in DMSO
3
4
(
2.0 mL) were irradiated with 2 × 3 W blue LEDs for 24 h in a sealed
a
Schlenk tube at room temperature, unless otherwise noted. Deter-
mined by H NMR.
1
substituted 2-(1-arylvinyl)anilines proceeded smoothly with
bromocyclobutane 2i and atmospheric pressure CO to afford
2
light irradiation, which is oxidized by alkyl bromide 2 to
generate active Pd(I) species B and an alkyl radical.
Meanwhile, with the assistance of TBD, the o-alkenylaniline
6
-, 7-, and 8-substituted 1,4-dihydro-2H-3,1-benzoxazin-2-ones
in moderate to good yields. The electronic properties of the
substituents on the phenyl ring of the aniline moiety had some
effect on the reaction. For example, the substrates bearing
electron-donating (4a−4f, 75%−80%) and weak electron-
withdrawing groups (4i−4j, 66%−81%) worked well. How-
ever, for substrates possessing a strong electron-withdrawing
group on the aniline moiety, no desired product 4k could be
detected. Notably, some functional groups, such as methyl (4a,
1a reacts with CO
rapidly, leading to carbamate C.
2
Meanwhile, the addition of the radical to the alkene in
carbamate C produces a more stabilized benzylic radical D.
Then, the SET between Pd(I) species and intermediate D
regenerates the Pd(0) catalyst and delivers the stabilized
carbon-cation species E. Finally, intramolecular nucleophilic
attack of intermediate E affords 1,4-dihydro-2H-3,1-benzox-
azin-2-one 3a.
In conclusion, we have developed a visible-light-driven
palladium catalyzed radical oxy-alkylation of 2-(1-arylvinyl)-
anilines with unactivated alkyl bromides and CO , affording a
2
6
8
6%), methoxy (4b, 76%), methylthio (4e, 67%), fluoro (4i,
0%), and chloro (4j, 66%) groups, all remained untouched
under these reactions. Importantly, by replacing the phenyl
with 2-thiophenyl, 2-furanyl, and 2-naphthyl, the desired
products 4m, 4n, and 4o could be isolated in 65%, 26%, and
2
3% yields, respectively. Unfortunately, introducing a methyl
to vinyl resulted in the low yield (4p, 28%, dr = 1/1.15), which
would be attributed to the steric hindrance.
Some control experiments were conducted to gain insight
into this transformation. In the presence of radical scavenger
series of 1,4-dihydro-2H-3,1-benzoxazin-2-ones in moderate to
excellent yields. This procedure starts with the carboxylation of
an amino by CO . Then, under visible light, the reaction of
2
alkyl bromides and a palladium catalyst produces an alkyl
radical, which undergoes the addition to the vinyl to form a
new radical species. After the single electron transfer (SET)
oxidation of the newly formed radical species to a carbocation,
the cyclization takes place whereby intramolecular nucleophilic
attack of the carboxylate anion to the carbocation occurs.
Thus, it represents an efficient method for incorporation of
2
,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO, 3 equiv), the
reaction was totally inhibited, and radical adduct 5 was
detected by GC-MS (Scheme 2a; for details, please see
Supporting Information). Thus, this reaction may involve a
radical pathway. Moreover, a radical clock experiment was
conducted by using cyclopropylmethyl bromide 2p as the
alkylation reagent. As expected, the reaction of 1a, CO , and
2
2
p formed the rearranged product 3p in 32% yield (Scheme
CO into heterocycles.
2
C
DOI: 10.1021/acs.orglett.9b02700
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
2
3
Martin, R. Ni-Catalyzed Carboxylation of C(sp )- and C(sp )-O
ASSOCIATED CONTENT
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(PDF)
Accession Codes
CCDC 1920540 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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Form Formamides, Aminals, and Methylamines. Angew. Chem., Int.
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́
̃
AUTHOR INFORMATION
Corresponding Author
■
*
(
+)- and (−)-Protected 5-Aminomethyl-1,3-oxazolidin-2-one Deriv-
atives from Allylamine and Carbon Dioxide. Tetrahedron: Asymmetry
E-mail: jiangcheng@cczu.edu.cn.
ORCID
2
006, 17, 2548−2557. (b) Takeda, Y.; Okumura, S.; Tone, S.; Sasaki,
I.; Minakata, S. Cyclizative Atmospheric CO Fixation by Unsaturated
Amines with t-BuOI Leading to Cyclic Carbamates. Org. Lett. 2012,
2
Song Sun: 0000-0002-9974-6456
Jin-Tao Yu: 0000-0002-0264-9407
Jiang Cheng: 0000-0003-2580-1616
Notes
1
4, 4874−4877. (d) Ye, J.-H.; Song, L.; Zhou, W.-J.; Ju, T.; Yin, Z.-B.;
Yan, S.-S.; Zhang, Z.; Li, J.; Yu, D.-G. Selective Oxytrifluoromethy-
lation of Allylamines with CO . Angew. Chem., Int. Ed. 2016, 55,
0022−10026.
4) (a) Sekine, K.; Kobayashi, R.; Yamada, T. Silver-catalyzed Three-
component Reaction of Propargylic Amines, Carbon Dioxide, and N-
Iodosuccinimide for Stereoselective Preparation of (E)-Iodovinylox-
azolidinones. Chem. Lett. 2015, 44, 1407−1409. (b) Hu, J.; Ma, J.;
Zhu, Q.; Zhang, Z.; Wu, C.; Han, B. Transformation of Atmospheric
CO Catalyzed by Protic Ionic Liquids: Efficient Synthesis of 2-
Oxazolidinones. Angew. Chem., Int. Ed. 2015, 54, 5399−5403.
c) Ishida, T.; Kobayashi, R.; Yamada, T. Novel Method of Tetramic
Acid Synthesis: Silver-Catalyzed Carbon Dioxide Incorporation into
Propargylic Amine and Intramolecular Rearrangement. Org. Lett.
014, 16, 2430−2433. (d) García-Domínguez, P.; Fehr, L.; Rusconi,
G.; Nevado, C. Palladium-Catalyzed Incorporation of Atmospheric
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(
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China
Nos. 21602019, 21572025, and 21672028), “Innovation &
Entrepreneurship Talents” Introduction Plan of Jiangsu
Province, Natural Science Foundation of Jiangsu Province
BK20171193), Jiangsu Key Laboratory of Advanced Catalytic
Materials & Technology (BM2012110), and Advanced
Catalysis and Green Manufacturing Collaborative Innovation
Center for financial support.
■
(
2
(
(
2
CO : Efficient Synthesis of Functionalized Oxazolidinones. Chem. Sci.
2
2
016, 7, 3914−3918.
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DOI: 10.1021/acs.orglett.9b02700
Org. Lett. XXXX, XXX, XXX−XXX