Utilization of CO2 as a C1 Building Block in a Tandem Asymmetric A3 Coupling-Carboxylative Cyclization Sequence to 2-Oxazolidinones

Article abstract of DOI:10.1021/acscatal.7b03370

We report a tandem asymmetric aldehyde-alkyne-amine (A³) coupling-carboxylative cyclization sequence for the highly enantioselective synthesis of chiral N-aryl 2-oxazolidinones. This is a rare example of a multicatalyst-promoted asymmetric tand

Full text of DOI:10.1021/acscatal.7b03370

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Letter
Utilization of CO2 as a C1 Building Block in a Tandem Asymmetric A3
Coupling-Carboxylative Cyclization Sequence to 2-Oxazolidinones
Xiao-Tong Gao, Chen-Chen Gan, Si-Yue Liu, Feng Zhou, Hai-Hong Wu, and Jian Zhou
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.7b03370 • Publication Date (Web): 14 Nov 2017
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ACS Catalysis
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Utilization of CO2 as a C1 Building Block in a Tandem Asymmetric A3
Coupling-Carboxylative Cyclization Sequence to 2-Oxazolidinones
XiaoꢀTong Gao,† ChenꢀChen Gan,† SiꢀYue Liu,‡ Feng Zhou*,† HaiꢀHong Wu*,† and Jian Zhou*,†,§,║
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†
§
Shanghai Key Laboratory of Green Chemistry and Chemical Process and Shanghai Engineering Research Center of
Molecular Therapeutics and New Drug Development, East China Normal University, 3663N Zhongshan Road, Shanghai
200062, P. R. China.
‡ College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, P. R. China
║ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, P R China.
ABSTRACT: We report a tandem asymmetric aldehyde–alkyne–amine (A3) couplingꢀcarboxylative cyclization sequence for the
highly enantioselective synthesis of chiral Nꢀaryl 2ꢀoxazolidinones. This is a rare example of a multicatalystꢀpromoted asymmetric
tandem reaction using CO2 as a C1 synthon. Notably, the copper species and ligand from the upstream A3 reaction are internally
reused to facilitate the downstream silverꢀcatalyzed carboxylative cyclization.
KEYWORDS CO2 transformation, Asymmetric tandem reaction, Carboxylative cyclization, A3 coupling, 2-Oxazolidinone
Utilization of carbon dioxide (CO2) as an inexpensive, nonꢀ
toxic and renewable C1 feedstock has attracted everꢀ
increasing attention worldwide in the past decade. This not
only provides a promising complement to carbon capture and
storage but offers the promise to develop costꢀeffective protoꢀ
cols to valueꢀadded chemicals.1 However, although a variety
of elegant reactions using CO2 as C1 synthon have been deꢀ
veloped, the merger of CO2 chemical fixation into catalytic
asymmetric tandem reactions for the synthesis of chiral comꢀ
pounds of important applications is largely undeveloped.2,3
As an important class of heterocycles, 2ꢀoxazolidinones
have wide applications in organic synthesis, pharmaceutical
chemistry and agrochemistry.4 Among their known synthetic
methods,5 those based on CO2 are very attractive,6 and in parꢀ
ticular, the carboxylative cyclization of propargylamines and
CO2 has developed quickly since the seminal work of Mitsudo
and Watanabe (Scheme 1A).7,8 Besides the elegant catalystꢀ
free protocols disclosed by the groups of Ikariya9 and Han10
using supercritical CO2 and an ionic liquid system at elevated
temperature, respectively, the use of metal catalysts to realize
this reaction at mild conditions is of current interest. For exꢀ
ample, Yamada reported that silver salts could catalyze this
reaction under mild conditions.11 Meanwhile, copper12a–c, palꢀ
ladium12d–g and gold12h–j catalysis also showed their value.
Despite significant achievements, the synthesis of chiral 2ꢀ
oxazolidinones via cyclization of propargylamines and CO2
remains unexplored.7–12 Most known catalytic protocols are
limited to Nꢀalkyl propargylamines, and only a highly active
Scheme 1. Carboxylative Cyclization of Propargylamine
On the other hand, chiral Nꢀaryl propargylanilines can be
readily obtained via catalytic asymmetric A3 coupling reacꢀ
tion.14 The development of carboxylative cyclization of Nꢀaryl
propargylamine and CO2, in combination with an asymmetric
A3 coupling reaction, would provide a highly efficient strategy
for the oneꢀpot synthesis of chiral Nꢀaryl 2ꢀoxazolidinones
from simple starting materials (Scheme 1B). Here, we wish to
report our efforts in developing such an unprecedented tandem
asymmetric A3 couplingꢀcarboxylative cyclization sequence.
We began by investigating the carboxylative cyclization of
Nꢀphenyl propargylamine 4a under a CO2 pressure of 1.0 MPa.
Known metal catalysts for the corresponding reaction of Nꢀ
alkyl propargylamines were first examined.11,12 Not surprisingꢀ
Nꢀaryl propargylamine with
a terminal alkyne worked
(Scheme 1A).12g Possibly, Nꢀaryl propargylamines undergo
alkyne hydroarylation more easily than CO2 incorporation as a
result of the lower nucleophilicity of the nitrogen atom. This is
further supported by the fact that under Ag(I), Cu(I) and Au(I)
catalysis, Nꢀaryl propargylamines readily undergo cycloisomꢀ
erization.13
ly, (IPr)AuCl12h and Pd(OAc)2 as the catalyst afforded only
the undesired hydroarylation adduct 6 (entries 1, 2, Table 1).
12e
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CuI mixed with DBU12c was inactive (entry 3), and the most
Page 2 of 5
efficient known catalyst, AgOAc/DBU,11b failed as well (entry
4). Considering that organic bases played an important role in
the Agꢀcatalyzed versions, to facilitate the incorporation of the
CO2 to form the carbamate and to serve as a ligand to tune the
catalytic property of Ag(I),11d,e we optimized different organic
bases. To our delight, the use of 1,3ꢀdiphenylguanidine (DPG)
significantly accelerated the desired cyclization, affording 2ꢀ
oxazolidinone 5a in 54% yield within 24 h, without the detecꢀ
tion of byproduct 6 by NMR analysis of the reaction mixture
(entry 6). Further studies revealed that both DMF and 1,2ꢀ
dichloroethane (DCE) were suitable solvents (entries 6–8).
While reaction in DMF resulted in a slightly higher yield,
DCE was chosen as the optimal solvent, as it was also suitable
for A3 coupling. After evaluating different silver salts, AgOBz
proved to be the most promising, affording 5a in 70% yield
(entries 8–12).
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2
3
4
5
6
7
8
Having established the conditions for the two distinct cataꢀ
lytic reactions, we next tried combining both into a oneꢀpot
tandem synthesis, to save time, labor and resources and to
avoid yield losses associated with the purification of chiral
amines 4. It is worth mentioning that the merger of both steps
into one pot was not as trivial as it first appeared because the
catalyst and the excess reagents from the first step might deacꢀ
tivate the catalyst of the next step, a wellꢀknown challenge in
developing a multicatalyst promoted asymmetric tandem reacꢀ
tion (MPATR)17. Although DCE was identified as a suitable
solvent for both steps based on our experience on MPATR,18 it
was apparent that the alkyne, usually used in excess for A3
reactions,14–16 would interfere with AgOBz for the cyclization
due to a strong soft–soft interaction. Accordingly, control exꢀ
periments were conducted to evaluate the influence of each
reaction component of the A3 reaction on the AgOBzꢀ
catalyzed cyclization.
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Table 1. Carboxylative Cyclization Reaction
Yield (%)a
Time
Entry
Cat.
Base Solvent
Table 2. Control Experiments
(h)
5a
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
54
10
45
60
25
35
70c
6
1b
2b
3b
4
(IPr)AuCl
Pd(OAc)2
CuI
ꢀꢀꢀ
ꢀꢀꢀ
CH3OH
Toluene
24
24
24
24
24
24
24
36
36
36
36
36
80
25
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
ꢀꢀꢀ
DBU DMSO
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
DBU
TMG
DPG
DMF
DMF
DMF
Entry
Additive
None
X
ꢀꢀꢀ
Yield (%)a
5
1
2
3
4
5
6
7
8
45
20
53
97
98
90
97
90
6
Phenylacetylene (2a)
Aniline (3a)
Cu(OTf)2
CuOTf
50
7
DPG Toluene
20
8
DPG
DCE
DCE
DCE
DCE
DCE
10
9
AgClO4·H2O DPG
10
10
11
AgOTf
AgTFA
AgOBz
DPG
DPG
DPG
L
12
CuOTf/L
10/12
10/12
12
Cu(OTf)2/L
a
1
Determined by H NMR using mesitylene as internal standard.
a Isolated yield.
b
o
c
50 C. Isolated yield. Note: 4a was not fully consumed in enꢀ
tries 6–12. DBU = 1,8ꢀDiazabicyclo[5.4.0]undecꢀ7ꢀene. TMG =
1,1,3,3ꢀTetramethylguanidine. DPG = 1,3ꢀDiphenylguanidine.
For a rapid comparison, all reactions were quenched after
24 h. Without any additive, AgOBzꢀcatalyzed cyclization afꢀ
forded 5a in 45% yield (entry 1, Table 2). As expected, the
presence of 50 mol% of phenylacetylene 2a severely retarded
the reaction, giving 5a in only 20% yield (entry 2), possibly
due to the competitive binding of 2a and 4a to Ag(I). The adꢀ
dition of 20 mol% aniline 3a improved the yield to 53% (entry
3). This was in accordance with literature reports that primary
amines could react with CO2 to form carbamic acid to enhance
the effective concentration of CO2 in solution, helpful for carꢀ
boxylative cyclization.12a,b Very surprisingly, the addition of
Cu(OTf)2 strongly accelerated the Agꢀcatalyzed cyclization to
complete within 24 h to afford 5a in 97% yield (entry 4). We
further tested the effect of CuOTf as the additive because it
might be generated in situ in the A3 reaction,19 and a similar
hastening effect was observed (entry 5). An obvious ligandꢀ
acceleration effect20 took place when L was added to the Agꢀ
catalyzed cyclization (entry 6). In contrast, without any addiꢀ
Meanwhile, we investigated the catalytic enantioselective
A3 reaction to synthesize chiral Nꢀaryl propargylamine 4a. The
criterion for our screening was that the A3 reaction must be run
in DCE, to coordinate with carboxylative cyclization to form
our designed tandem sequence shown in Scheme 1B. It should
be noted that although remarkable progress has been made in
the catalytic asymmetric A3 reaction since the pioneering work
of Li et al.,15 most protocols relied on the use of airꢀsensitive
and costly Cu(I) salts such as CuOTf and CuPF6, with very
limited examples based on airꢀstable Cu(II) salts.16 We sucꢀ
cessfully found our new PYBOX ligand L in combination
with Cu(OTf)2 worked well in the A3 reaction of aldehyde 1a,
phenylacetylene 2a and aniline 3a in DCE at 25 °C, giving
propargylamine 4a in 98% yield and 94% ee. For details, see
supporting information.
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ACS Catalysis
tive, the cyclization did not complete even after 36 h (entry 12, The results shown in Tables 2 and 3 are very interesting,
1
2
3
4
5
6
7
8
Table 1). Furthermore, no matter adding CuOTf/L or
Cu(OTf)2/L, the yield of 5a was substantially enhanced to 97%
and 90%, respectively (entries 7, 8).
suggesting that the copper species, ligand and remaining aniꢀ
line from the upstream A3 reaction, but not alkyne, could be
internally reused to facilitate the downstream silverꢀcatalyzed
cyclization. Although a detailed explanation of the acceleraꢀ
tion effect in the Agꢀcatalyzed carboxylative cyclization
awaits further studies, it is worth mentioning that this protocol
constitutes a rare example of asymmetric tandem reactions
capable of internally recycling residue from the upstream step
to facilitate the downstream reaction.21 Despite some elegant
tandem sequences can internally reuse byproduct and/or exꢀ
cess reagent, this newly developed sequence first demonstrates
that the remaining catalyst from the upstream step could serve
as a cocatalyst or additive to improve greatly the efficiency of
the downstream step.
Based on the above control experiments, we speculated that
the key to develop the desired tandem sequence was to avoid
the use of excess alkyne in the A3 coupling step. With this in
mind, we then optimized the condition to integrate both steps
into a oneꢀpot operation. The initial Cuꢀcatalyzed A3 coupling
was run in air at 25 °C in DCE for 15 h till the full conversion
of aldehyde, and then AgOBz and DPG were added for the
next cyclization with a CO2 pressure of 1.0 MPa at 25 °C. As
expected, when decreasing the use of alkyne 2a from 1.5 to
1.2 and 1.0 equiv for the A3 reaction, the yield of the desired
2ꢀoxazolidinone 5a was improved from 40% to 68% and 92%,
respectively, without erosion of ee value (entries 1–3, Table 3).
Interestingly, when decreasing the usage of 2a from 1.5 to 1.0
equiv for A3 reaction, our new ligand L afforded similar yield
whilst the use of A and B resulted in obviously diminished
yield.22 Under this condition, reducing the loading of AgOBz
to 10 mol% resulted in the diminished 40% yield of 5a (entry
4). However, if lowering the loading of DPG to 50 mol%, the
sequence could still afford 5a in 97% yield if running the cyꢀ
clization step for 36 h (entry 5), but further lowering its use to
20 mol% led to greatly diminished yield (entry 6). It should be
noted that no cyclization occurred if either AgOBz or DPG
was absent (entries 7, 8), so the absence of both, suggests copꢀ
per species from the A3 step were unable to mediate the subseꢀ
quent cyclization. We also conducted the tandem reaction
under 0.1 MPa of CO2, and found the reaction proceeded in a
much slower rate. Even the cyclization step was run for 72 h,
product 5a was still obtained in only 25% and 58% yield, reꢀ
spectively, in the presence of 50 mol% or 100 mol% of DPG
(entries 9ꢀ10).
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10
11
12
13
14
15
16
17
18
19
20
21
22
23
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25
26
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Table 4. Substrate Scope of the Tandem Reaction
Enꢀ
try
Yield Ee
(%)a (%)b
1 (R1)
2 (R2)
3 (Ar)
5
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
97
91
91
97
90
96
90
85
82
87
90
84
90
90
84
95
99
99
44
85
82
94
86
92
97
94
96
96
96
96
96
95
94
96
90
91
94
92
94
92
93
93
96
91
92
94
95
92
94
94
5a
5b
5c
5d
5e
5f
4ꢀMeC6H4
4ꢀEtC6H4
4ꢀClC6H4
4ꢀBrC6H4
4ꢀFC6H4
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3ꢀMeC6H4
3ꢀBrC6H4
2ꢀMeC6H4
Ph
Ph
5g
5h
5i
Ph
Ph
Table 3. Condition Optimization for Tandem Reaction
Ph
PMP
Ph
Ph
O
2a (X equiv)
10 3,4ꢀ(Me)2C6H3
Ph
5j
Ph
N
O
Ph NH2
Cu
Ag
Ph CHO
+
11
12
13
14
15
16
17
18
19
20
21
22
23
24c
25c
2ꢀnaphthyl
Ph
Ph
Ph
5k
5l
1a (0.20 mmol)
3a (0.24 mmol)
Ph
5a (94% ee)
Ph
CO2
One-pot sequential!
PMP
4ꢀMeC6H4
4ꢀFC6H4
4ꢀClC6H4
4ꢀBrC6H4
3ꢀClC6H4
2ꢀClC6H4
CH3(CH2)4
Ph
Ph
Cu(OTf)2 (10 mol%)
Ph
Ph
AgOBz (Y mol%)
DPG (Z mol%)
5m
5n
5o
5p
5q
5r
5s
Ph
Ph
NH
L (12 mol%)
Ph
Ph
CO2, DCE, 25 oC
DCE, 25 oC, 15 h
Ph
4a
Ph
Ph
AgOBz DPG
CO2
(MPa)
Time Yield
Ph
Ph
2a
(X)
Entry
(Y)
20
20
20
10
20
20
ꢀꢀꢀ
20
20
20
(Z)
100
100
100
100
50
(h)
24
24
24
24
36
24
24
24
72
72
(%)a
40
68
92
40
97
21
ꢀꢀꢀ
ꢀꢀꢀ
25
58
Ph
Ph
1
2
1.5
1.2
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.1
0.1
Ph
Ph
Ph
PMP
PMP
4ꢀMeC6H4
4ꢀEtC6H4
3ꢀMeC6H4
3ꢀFC6H4
3ꢀBrC6H4
3
Ph
5t
4
Ph
Ph
5u
5v
5w
5x
5y
5
Ph
Ph
6
20
Ph
Ph
7
20
Ph
Ph
8
ꢀꢀꢀ
Ph
Ph
9
50
84
(1.1g)
26d
Ph
Ph
Ph
94
5a
10
100
a Isolated yield. b Determined by chiral HPLC analysis. c 50 oC for
a Isolated yield.
d
the cyclization step. On a 4.0 mmol scale, 5 mol% of Cu(OTf)2
for the A3 reaction.
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Next, we evaluated the scope of this tandem asymmetric A3
couplingꢀcarboxylative cyclization sequence with respect to
different aldehydes, alkynes and anilines under the optimized
conditions (Table 4). First, aryl aldehydes with either electronꢀ
withdrawing or ꢀdonating substituents worked well to afford
chiral 2ꢀoxazolidinones 5a–j in 82–97% yield and 90–96% ee
(entries 1–10). 2ꢀNaphthaldehyde also furnished the desired
product 5k in 90% yield and 91% ee (entry 11). Second, both
aryl and alkyl alkynes were all viable substrates. Aryl alkynes
with different substituted phenyl groups provided the desired
adducts 5l–r in 84–99% yield with 92–96% ee (entries 12–18).
Aliphatic 1ꢀheptyne also gave the corresponding product 5s in
91% ee, albeit with diminished 44% yield (entry 19). Finally,
primary arylamines with electronꢀrich, ꢀneutral and ꢀdeficient
groups on the phenyl ring were also examined. The desired 2ꢀ
oxazolidinones 5t–y were readily obtained in high to excellent
yields and ee values (entries 20–25). The scalability of the
tandem reaction was further shown by a 4.0 mmol scale reacꢀ
tion using 5 mol% of copper catalyst, affording chiral 2ꢀ
oxazolidinone 5a in 84% yield and 94% ee (entry 26).22 Howꢀ
ever, aliphatic primary amines and aliphatic aldehydes are not
compatible under this condition. This is not surprising, since
both still presented as challenging substrates in the A3 couꢀ
pling reaction.14–16 The absolute configuration of the chiral 2ꢀ
oxazolidinone 5e was determined to be R by Xꢀray analysis.23
In summary, we have developed a novel tandem asymmetꢀ
ric A3 couplingꢀcarboxylative cyclization sequence for the
facile synthesis of chiral Nꢀaryl 2ꢀoxazolidinones with excelꢀ
lent ee values under mild conditions. This process constitutes a
rare example of MPATR using CO2 as a C1 synthon, as well
as catalytic carboxylative cyclization of Nꢀaryl propargylaꢀ
mines and CO2. The key to the efficiency of the sequence is
that the copper species and ligand from the upstream A3 reacꢀ
tion are internally reused to facilitate the downstream Agꢀ
catalyzed carboxylative cyclization. The development of novel
CO2ꢀparticipated MPATR are now in progress in our laboratoꢀ
ry.
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ASSOCIATED CONTENT
Supporting Information.
Experimental details, optimization of reaction conditions, characꢀ
terization of products, Xꢀray data of 5e, copies of NMR and
HPLC spectra of all products. This material is available free of
charge via the internet at http://pubs.acs.org.
(4) (a) Barbachyn, M. R.; Ford, C. W. Angew. Chem., Int. Ed. 2003,
42, 2010–2023. (b) Mukhtar, T. A.; Wright, G. D. Chem. Rev. 2005,
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AUTHOR INFORMATION
Corresponding Author
(6) For reviews: (a) Pulla, S.; Felton, C. M.; Ramidi, P.; Gartia, Y.;
Ali, N.; Nasini, U. B.; Ghosh, A. J. CO2 Util. 2013, 2, 49–57. (b) Liu,
X.ꢀF.; Wang, M.ꢀY.; He, L.ꢀN. Curr. Org. Chem. 2017, 21, 698–717.
(c) Zhang, W.; Zhang, N.; Guo, C.; Lu, X. Chin. J. Org. Chem. 2017,
37, 1309–1321. For examples: (d) Song, Q.ꢀW.; Yu, B.; Li, X.ꢀD.; Ma,
R.; Diao, Z.ꢀF.; Li, R.ꢀG.; Li, W.; He, L.ꢀN. Green Chem. 2014, 16,
1633–1638. (e) Zhang W.ꢀZ.; Xia, T.; Yang, X.ꢀT.; Lu, X.ꢀB. Chem.
Commun. 2015, 51, 6175–6178. (f) Adhikari, D.; Miller, A. W.; Baik,
M.ꢀH.; Nguyen, S. T. Chem. Sci. 2015, 6, 1293–1300. (g) Yamashita,
K.; Hase, S.; Kayaki, Y.; Ikariya, T. Org. Lett. 2015, 17, 2334–2337.
(h) Sharma, S.; Singh, A. K.; Singh, D.; Kim, D.ꢀP. Green Chem.
2015, 17, 1404–1407. (i) Ye, J.ꢀH.; Song, L.; Zhou, W.ꢀJ.; Ju, T.; Yin,
Z.ꢀB.; Yan, S.ꢀS.; Zhang, Z.; Li, J.; Yu, D.ꢀG. Angew. Chem., Int. Ed.
2016, 55, 10022–10026. (j) Zhou, F.; Xie, S.ꢀL.; Gao, X.ꢀT.; Zhang,
R.; Wang, C.ꢀH.; Yin, G.ꢀQ.; Zhou, J. Green Chem. 2017, 19, 3908–
3915.
* Eꢀmail for F. Zhou: fzhou@chem.ecnu.edu.cn
* Eꢀmail for H. H. Wu: hhwu@chem.ecnu.edu.cn
* Eꢀmail for J. Zhou: jzhou@chem.ecnu.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
Financial support from 973 Program (2015CB856600) and NSFC
(21502053, 21573073, 21472049, 21725203) is appreciated.
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(22) As kindly suggested by one of the reviewers, we compared the
potency of our ligand L with unmodified PYBOX A and B in the A3
reaction when using only 1.0 equiv of alkyne 2a. This result further
suggested the superiority of our ligand L.
2a L (R = OBn, R1 = Ph) A (R = H, R1 = Ph) B (R = H, R1 = iꢀPr)
(X) Yield (%) Ee (%) Yield (%) Ee (%) Yield (%) Ee (%)
1.5
1.0
98
97
94
94
98
78
91
90
82
60
60
61
(23) The Xꢀray crystal structure information is available at the
Cambridge Crystallographic Data Centre (CCDC) under deposition
numbers CCDCꢀ1571692 (5e). The data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif
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