Asymmetric [3+2] Cycloaddition of Olefins with Morita-Baylis-Hillman Carbonates Catalyzed by BINOL-Based Bifunctional Phosphine

Article abstract of DOI:10.1055/s-0037-1611752

We have developed a series of novel BINOL-based phosphines. These bifunctional organocatalysts can be used in the [3+2] cycloaddition of electron-deficient olefins and Morita-Baylis-Hillman (MBH) carbonates. Moderate to excellent yields (up to >99%) and good to excellent enantioselectivities (up to 95% ee) can be obtained in the cycloaddition reaction of maleimides and MBH carbonates. The application of these novel phosphines can be further extended to the asymmetric synthesis of chiral spirooxindoles (up to 85% ee). The results in this study indicate that the BINOL moiety plays an important role in stereocontrol.

Full text of DOI:10.1055/s-0037-1611752

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© Georg Thieme Verlag Stuttgart · New York
2019, 30, A–F
letter
A
en
H.-L. Cui et al.
Letter
Synlett
Asymmetric [3+2] Cycloaddition of Olefins with Morita–Baylis–
Hillman Carbonates Catalyzed by BINOL-Based Bifunctional
Phosphine
Hai-Lei Cui*a
Xue Tanga,b
Meng-Fan Lia
Xing-Jie Xua,c
Yin Shia
0
0
0
0-
0
0
0
2-8
2
4
8-6
6
2
7
NC
O
CN
N
R1
R3
O
COOtBu
NC
NC
N
O
O
H
H
OBoc
Ph
PMB
R2
catalyst (10 mol%)
m-xylene, 35 °C
catalyst (10 mol%)
m-xylene, rt
R1
EWG
PPh2
GWE
N
R3
O
R2
N
a Laboratory of Asymmetric Synthesis, Chongqing Uni-
versity of Arts and Sciences, 319 Honghe Ave.,
Yongchuan, Chongqing, 402160, P. R. of China
cuihailei616@163.com
b School of Pharmacy, Chengdu University of Traditional
Chinese Medicine, Chengdu 611137, P. R. of China
c Key Laboratory of Molecular Target & Clinical
Pharmacology, School of Pharmaceutical Sciences &
the Fifth Affiliated Hospital, Guangzhou Medical
University, Guangzhou, Guangdong 511436, P. R. of
China
R2
O
PMB
15 examples
6 examples
O
up to >99% yield
up to 95% ee
up to 93% yield
up to 85% ee
N
H
catalyst
ONs
ONs
Ns: 4-NO2PhSO2
Received: 15.01.2019
Accepted after revision: 08.02.2019
Published online: 06.03.2019
phosphines based on the combination of Lewis base and
Brønsted acid. These BINOL-derived catalysts have been
used widely in asymmetric aza-Morita–Baylis–Hillman
(MBH) reactions and the transformations of MBH deriva-
tives.3a–e Later, Sasai and Ito independently reported their
studies on the development of BINOL-based chiral phos-
phines.3f,3g These new bifunctional phosphines were found
to be efficient catalysts that enabled aza-MBH reactions to
proceed with high levels of enantiocontrol. In 2007, the
Miller group reported an asymmetric version of Lu’s [3+2]
cycloaddition of allenoate esters and enones mediated by
an -amino acid based multifunctional phosphine.4 Jacobsen
et al. have prepared a new family of phosphinothiourea cat-
alysts for the enantioselective imine-allene [3+2] cycloaddi-
tion, affording substituted 2-aryl-2,5-dihydropyrroles.5
Zhao and co-workers developed simple bifunctional N-acyl
aminophosphines that could efficiently promote the asym-
metric [3+2] cycloaddition of allenoates and activated ole-
fins.6 The Lu group has designed a variety of amino acid-
based phosphines and many attractive methodologies have
been developed based on these novel phosphines.7 Notably,
the dipeptidic backbone-derived phosphine catalysts have
shown a fascinating capacity to provide stereochemical
control in a wide range of asymmetric reactions. Zhang and
co-workers reported a ferrocene-derived bifunctional phos-
phine-catalyzed asymmetric [4+2] cycloaddition of alle-
nones and enones.8 These novel catalysts have significantly
broadened the application scope of phosphines as organo-
catalysts in the field of organic synthesis. As a result of
these achievements, various new methodologies and com-
plex chiral molecules of great importance have been created.
DOI: 10.1055/s-0037-1611752; Art ID: st-2019-v0027-l
Abstract We have developed a series of novel BINOL-based phos-
phines. These bifunctional organocatalysts can be used in the [3+2] cy-
cloaddition of electron-deficient olefins and Morita–Baylis–Hillman
(MBH) carbonates. Moderate to excellent yields (up to >99%) and good
to excellent enantioselectivities (up to 95% ee) can be obtained in the
cycloaddition reaction of maleimides and MBH carbonates. The applica-
tion of these novel phosphines can be further extended to the asym-
metric synthesis of chiral spirooxindoles (up to 85% ee). The results in
this study indicate that the BINOL moiety plays an important role in ste-
reocontrol.
Key words BINOL, phosphine, organocatalyst, Morita–Baylis–Hillman
derivative, cycloaddition
The past few years have witnessed great progress in the
field of phosphine catalysis. A range of powerful phosphine
catalysts have been designed and thus a large number of el-
egant asymmetric reactions have been disclosed.1 Conse-
quently, on the basis of these developments, easy construc-
tions of structurally diversified chiral molecules have been
realized. Accordingly, increasing attention has been paid to
the design and application of novel phosphine-based or-
ganocatalysts. Bifunctional organocatalysts as a combina-
tion of functional units enable two activation modes that
could activate both nucleophile and electrophile in the cat-
alytic system synergistically, thus providing enantioen-
riched molecules efficiently.2 Recently, several research
groups have made intensive efforts to design bifunctional
phosphine catalysts.3–9 For example, Shi and co-workers
disclosed their achievements on the design of bifunctional
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

B
H.-L. Cui et al.
Letter
Synlett
Steric effect
R'
PPh2
Nucleophilic phosphine
N
H
OR
OR
Steric effect by
introducing BINOL
Hydrogen-bonding activation
Steric effect (R = bulky group)
or hydrogen-bonding activation (R = H)
Figure 1 Our design for the BINOL-based bifunctional phosphine
Inspired by these pioneering achievements,3–9 we aimed
to design novel 1,1′-bi-2-naphthol (BINOL) derived bifunc-
tional catalysts for nucleophilic catalysis. As shown in Fig-
ure 1, our design principle is to combine BINOL and amino
phosphine, enabling further stereocontrol through steric ef-
fects and/or hydrogen-bonding interactions caused by a
modified BINOL moiety. The introduction of BINOL into
amino phosphines may provide effective steric effects as
well as hydrogen-bonding interactions, thus activating sub-
strates synergistically and achieving satisfactory levels of
enantiocontrol. In addition, the tunability of BINOL would
be beneficial for further novel catalyst design. Here, we re-
port our results on the design of novel BINOL-derived phos-
phine catalysts and their application in the [3+2] cycloaddi-
tion of MBH carbonates and electron-deficient olefins.
Initially, the [3+2] cycloaddition of electron-deficient
olefin N-phenyl maleimide 2a and MBH carbonate 3a was
selected as the model reaction to test the catalytic capabili-
ty of the newly designed catalysts.10–12 The Lu group and
the Shi group have employed dipeptide-based bifunctional
phosphine and multifunctional thiourea-phosphine, re-
spectively, to catalyze the same [3+2] cycloaddition reac-
tion, giving excellent enantioselectivities.10a,10b Very recent-
ly, Zhong and co-workers developed bifunctional ferrocen-
ylphosphines and excellent enantiocontrol was achieved
under the catalysis of the novel chiral phosphines.10c As
shown in Table 1, new urea-based catalyst 1a and BINOL-
derived catalysts 1b–c, developed in our group, were tested
and were found to be ineffective in this system (Table 1, en-
tries 1–3, <5% yields). We reasoned that methylene-teth-
ered catalyst lacked sufficient structural rigidity for enan-
tiocontrol. We then tested catalysts 1d–f, with an amide
group as linkage. The amide group in these catalysts linked
the phosphine moiety and the BINOL moiety, possibly gen-
erating the necessary chiral environment. As expected, bet-
ter enantiocontrol was achieved and excellent enantioselec-
tivities can be reached in the reactions catalyzed by 1d and
1e (entries 4 and 5, 97% ee and 94% ee, respectively). A trace
amount of product was observed when 1f was used as cata-
lyst, indicating that the hydroxyl groups of the BINOL moi-
ety failed to interact effectively with substrate through hy-
drogen-bonding, probably because of a side reaction with
MBH carbonate (entry 6). The use of catalyst 1g, bearing an
L-valinol backbone, afforded 82% ee, while D-valinol-de-
rived phosphine gave the opposite enantiomer of com-
pound 4a as the major isomer (entries 7 and 8, 82% ee ver-
sus –71% ee). As control experiment, catalyst 1i gave poor
ee value, indicating that the presence of BINOL is critical for
stereocontrol (entry 9, 10% ee). The obtained results sug-
gest that amino acid-derived backbones play a significant
role in the determination of absolute configuration, while
the BINOL unit in the catalyst is important for the genera-
tion of high enantioselectivity. The amide group is also es-
sential to tether the BINOL moiety and amino phosphine
moiety for enantiocontrol.
Further optimization studies were then conducted to
improve the yield and enantioselectivity. Higher reaction
temperature (50 °C) afforded better reaction yield and
slightly decreased ee value (entry 10, 64% yield, 94% ee).
Screening of solvent was then performed at 50 °C, but no
improvement on yield was achieved, although good enantio-
selectivities were obtained in all cases (entries 11–14, 90–
94% ee). It seems that the enantioselectivity is not sensitive
to the choice of solvent. The employment of two equiva-
lents of MBH carbonate 3a significantly increased the reac-
tion yield, while the use of an excess amount of N-phenyl
maleimide 1a led to reduced yield (entries 15 and 16, 21%
versus 91%). Further lowering the reaction temperature to
35 °C could slightly improve the reaction yield and enanti-
oselectivity (entry 17, 92% yield, 95% ee). The addition of 4
Å MS had a negative effect on reaction yield, while showing
no influence on ee value (entry 18, 85% yield, 95% ee).
Having established the optimized reaction conditions,
we next examined the generality of this catalytic system.
Good diastereoselectivities were observed in most cases
and we only isolated the major product in this study. As
shown in Scheme 1, variation of MBH carbonates on the
electron-withdrawing groups and phenyl ring was success-
ful. Both methyl and ethyl acrylate derived MBH carbonates
were employed successfully, giving excellent enantioselec-
tivities (Scheme 1, 4a and 4b, 95% ee and 93% ee, respec-
tively). Generally, good yields and enantioselectivities were
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

C
H.-L. Cui et al.
Letter
Synlett
Table 1 Optimization of Reaction Conditions of Asymmetric Synthesis of 4aa,b
O
O
H
H
OBoc
Catalyst
COOMe
MeOOC
N Ph
N
Ph
+
Ph
Ph
4a
O
O
3a
2a
Ph
H
N
H
O
S
N
N
Ph
PPh2
PPh2
PPh2
N
N
O
H
OR
OR
OR
OR
1a
1b R = H
1c R = Ts
1d R = Ns (4-NO2PhSO2)
1e R = Ts (4-MePhSO2)
1f R = H
O
O
PPh2
PPh2
N
N
H
H
Ph
O
ONs
ONs
ONs
ONs
PPh2
N
H
ONs
1g
1h
1i
Entry
Cat.
Sol
T (°C)
t (h)
drc
Yield (%)c
eed
1
2
1a
1b
1c
1d
1e
1f
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
m-xylene
THF
rt
20
20
21
23
20
20
20
20
23
6
–
<5
<5
<5
15
18
<5
40
33
5
–
–
rt
–
3
rt
–
<5
97
94
–
4
rt
>20:1
>20:1
–
5
rt
6
rt
7
1g
1h
1i
rt
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
82
–71
10
94
90
94
94
94
94
94
95
95
8
rt
9
rt
10
11
12
13
14
15e
16f
17f
18f,g
1d
1d
1d
1d
1d
1d
1d
1d
1d
50
50
50
50
50
50
50
35
35
64
20
12
35
25
21
91
92
85
6
DCE
6
PhCl
6
PhCF3
6
m-xylene
m-xylene
m-xylene
m-xylene
5
5
12
12
a Reaction conditions: 2a (0.05 mmol), 3a (0.06 mmol), catalyst (10 mol%) and solvent (0.5 mL).
b The yield of major product was determined by 1H NMR analysis using CH2Br2 as internal standard.
c Determined by 1H NMR spectroscopic analysis.
d Determined by HPLC analysis on a chiral stationary phase.
e Using 0.1 mmol of 2a and 0.05 mmol of 3a.
f Using 0.1 mmol of 3a (2 equiv).
g Adding 50 mg of 4 Å MS.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

D
H.-L. Cui et al.
Letter
Synlett
observed irrespective of the position of the substituents on
the phenyl ring (4c–g, 85–94% ee). However, the use of eth-
yl 2-(((tert-butoxycarbonyl)oxy)(p-tolyl)methyl)acrylate
gave a decreased yield (4e, 55% yield), suggesting the elec-
tron-donating group substituent of MBH carbonate has a
negative effect on the reaction yield. Aliphatic aldehyde de-
rived MBH carbonate gave lower yield compared with other
cases (4h, 16% yield, 90% ee). We reasoned that the instabil-
ity of the intermediate generated from catalyst and MBH
carbonate should be responsible for the low yield of com-
pound 4h. The employment of methyl and benzyl maleim-
ides afforded the corresponding bicyclic imides 4i–o in
moderate to excellent yields (44–99%) and good to excellent
ee values (88–94%).
attack triggered Michael–Michael–elimination cascade.
While transition mode B through Si-face attack and subse-
quent Michael–elimination cascade is disfavored because of
the steric repulsion of the Ns moiety next to the amide
group with the phenyl group of maleimide. In addition to
the hydrogen-bonding interaction provided by the amide
group in the catalyst, a - stacking effect may also exist in
the transition state between the naphthalene ring of the
catalyst and the maleimide.
To further investigate the catalytic effect of these BI-
NOL-based organocatalysts, [3+2] cycloaddition of isatin-
derived ,-dicyanoalkene and MBH carbonates was then
studied.7a,13 As shown in Scheme 3, spirooxindole 6 can be
obtained in good yields (69–93%) and good enantioselectiv-
ities (74–85% ee) in the presence of catalyst 1d.14 Good di-
astereoselectivities were also observed in most cases. These
results indicate that the BINOL-derived catalyst can be used
As shown in Scheme 2, we proposed a possible transi-
tion state for this reaction. Cycloaddition through transition
mode A would deliver the desired product 4a through Re-
O
H
O
OBoc
1d, m-xylene
GWE
N
R1
EWG
+
R1
R2
N
35 °C
H
R2
O
O
3
4
2
O
H
O
O
H
H
H
EtOOC
N Ph
ROOC
N
Ph
EtOOC
N Ph
H
Br
H
O
O
O
Br
4c, 15 h, 95%, 94% ee
4a, R = Me, 15 h, 75%, 95% ee
4b, R = Et, 15 h, 74%, 93% ee
4d, 14 h, 81%, 92% ee
O
H
O
H
O
H
EtOOC
N Ph
EtOOC
N Bn
EtOOC
N Ph
H
O
H
H
O
Me
O
4ha, 15 h, 16%, 90% ee
R
R
4e, R = Me, 15 h, 55%, 91% ee
4f, R = CN, 15 h, 95%, 89% ee
4g, R = NO2,14 h, 98%, 85% ee
4i, R = H, 16 h, 97%, 93% ee
4j, R = NO2, 14 h, >99%, 89% ee
O
H
O
H
EtOOC
N Me
EtOOC
N Me
H
Cl
H
O
O
R
4o, 14 h, 94%, 92% ee
4k, R = H, 16 h, >99%, 94% ee
4l, R = NO2, 14 h, 99%, 88% ee
4mb, R = Cl, 14 h, 80%, 89% ee
4n, R = Me, 15 h, 44%, 93% ee
Scheme 1 Examination of substrate scope. Reaction conditions: 2 (0.1 mmol), 3 (0.2 mmol) and 1d (10 mol%) in m-xylene (1.0 mL) at 35 °C. Isolated
yield of the major product given. The ee was determined by HPLC analysis on a chiral stationary phase. a Performed at 50 °C for 15 h; The yield of 4h was
determined by 1H NMR analysis using CH2Br2 as internal standard. b Relative configuration of compound 4m was determined according to reported
HPLC analysis results and other products were assigned by analogy.10b
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

E
H.-L. Cui et al.
Letter
Synlett
to promote the reaction successfully for the construction of
two contiguous quaternary centers and the introduction of
BINOL moiety is beneficial for controlling the stereochemis-
try.7a,13,14
novel phosphines to asymmetric reaction development and
to the synthesis of chiral heterocycles is under way in our
laboratory.
Funding Information
Ph
Ph
O
Ph
O
Ph
We are grateful for the support provided for this study by the National
Natural Science Foundation of China (21502013, 21871035) and
Ph
H
Ph
H
P
P
N
N
Chongqing University of Arts and Sciences (R2015BX01).
C
h
o
n
g
q
i
n
g
U
n
i
v
ersityofArts
a
n
d
S
c
i
e
n
c
es(R
2
0
1
5
B
X
0
1)Nati
o
n
a
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c
i
e
n
c
e
F
o
u
n
d
ati
o
n
of
C
h
i
n
a
(2
1
5
0
2
0
1
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o
n
a
lNaturalS
c
i
e
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c
e
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o
u
n
d
ati
o
n
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C
h
i
n
a
(2
1
8
7
1
0
3
5)
H
H
E
E
vs
ONs
ONs
ONs
ONs
O
R
O
R
N
Ph
N
Supporting Information
Ph
O
O
Supporting information for this article is available online at
A
B
https://doi.org/10.1055/s-0037-1611752.
S
u
p
p
orit
n
gInformati
o
n
S
u
p
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orit
n
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o
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disfavored
O
favored
O
References and Notes
H
H
MeOOC
N Ph
MeOOC
N Ph
(1) For reviews on phosphine catalysts, see: (a) Ni, H.; Chan, W.-L.;
Lu, Y. Chem. Rev. 2018, 118, 9344. (b) Guo, H.; Fan, Y. C.; Sun, Z.;
Wu, Y.; Kwon, O. Chem. Rev. 2018, 118, 10049. (c) Fan, Y. C.;
Kwon, O. Chem. Commun. 2013, 11588. (d) Li, W.; Zhang, J.
Chem. Soc. Rev. 2016, 45, 1657. (e) Wang, T.; Han, X.; Zhong, F.;
Yao, W.; Lu, Y. Acc. Chem. Res. 2016, 49, 1369. (f) Wei, Y.; Shi, M.
Acc. Chem. Res. 2010, 43, 1005. (g) Methot, J. L.; Roush, W. R. Adv.
Synth. Catal. 2004, 346, 1035. (h) Wang, Z.; Xu, X.; Kwon, O.
Chem. Soc. Rev. 2014, 43, 2927. (i) Xiao, Y.; Sun, Z.; Guo, H.;
Kwon, O. Beilstein J. Org. Chem. 2014, 10, 2089. (j) Xiao, Y.; Guo,
H.; Kwon, O. Aldrichimica Acta 2016, 49, 3.
H
H
Ph
O
Ph
O
4a
4a'
Scheme 2 Proposed transition modes
In conclusion, we have developed a series of novel BI-
NOL-derived organocatalysts. These multifunctional phos-
phines can be used in the [3+2] cycloaddition of electron-
deficient olefins and MBH carbonates. Moderate to excel-
lent yields (up to >99% yield) and good to excellent enanti-
oselectivities (up to 95%ee) can be obtained. The results ob-
tained in this study indicate that the BINOL moiety plays an
important role in stereocontrol. The application of these
(2) For reviews on bifunctional catalysis, see: (a) Paull, D. H.;
Abraham, C. J.; Scerba, M. T.; Alden-Danforth, E.; Lectka, T. Acc.
Chem. Res. 2008, 41, 655. (b) Matsunaga, S.; Shibasaki, M. Chem.
Commun. 2014, 1044.
COOtBu
NC
NC
CN
OBoc
NC
R2
O
COOtBu
1d, m-xylene
R1
R1
+
R2
O
N
N
rt
PMB
3
PMB
5
6
COOtBu
COOtBu
COOtBu
NC
NC
NC
NC
NC
NC
Cl
O
O
Br
O
N
N
N
Cl
PMB
PMB
PMB
6c, 15 h, 93%, 80% ee
6a, 18 h, 85%, 74% ee
6b, 45 h, 71%, 81% ee
COOtBu
COOtBu
COOtBu
NC
NC
NC
NC
NC
NC
Me
O
O
N
CN
O
N
N
PMB
PMB
PMB
6f, 35 h, 69%, 84% ee
6d, 13 h, 77%, 82% ee
6e, 13 h, 88%, 85% ee
Scheme 3 Application of BINOL-based catalysts for the synthesis of chiral spirooxindoles. Reaction conditions: 5 (0.1 mmol), 3 (0.2 mmol) and 1d (10
mol%) in m-xylene (1.0 mL) at r.t. Isolated yield of the major product given. The ee was determined by HPLC analysis on a chiral stationary phase.
Relative configuration of compound 6f was determined according to reported HPLC analysis results and other products were assigned by analogy.7a
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F

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H.-L. Cui et al.
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Synlett
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(14) For detailed optimization results, see the Supporting Informa-
tion
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–F