Organocatalytic desymmetrization of cyclic meso-anhydrides through enantioselective alcoholysis with functionalized primary nitroallylic alcohols

Article abstract of DOI:10.1016/j.tet.2014.10.008

The direct organocatalytic desymmetrization of cyclic meso-anhydrides was achieved by alcoholysis with nitroallylic alcohols. The reaction between primary nitroallylic alcohols and cyclic meso-anhydrides catalyzed by cinchonidine derived thiourea organoca

Full text of DOI:10.1016/j.tet.2014.10.008

Tetrahedron 70 (2014) 9064e9069
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Organocatalytic desymmetrization of cyclic meso-anhydrides
through enantioselective alcoholysis with functionalized primary
nitroallylic alcohols
*
Yan ming Chen, Mamatha Amireddy, Kwunmin Chen
Department of Chemistry, National Taiwan Normal University, Taipei 116, Taiwan, ROC
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 22 August 2014
Received in revised form 25 September 2014
Accepted 4 October 2014
Available online 13 October 2014
The direct organocatalytic desymmetrization of cyclic meso-anhydrides was achieved by alcoholysis with
nitroallylic alcohols. The reaction between primary nitroallylic alcohols and cyclic meso-anhydrides
catalyzed by cinchonidine derived thiourea organocatalyst II (10 mol %) proceeded smoothly. The cor-
responding hemiesters were obtained in high chemical yields with high to excellent levels of stereo-
selectivity (up to 90% yield and 99% ee). On the other hand, the reversal of enantioselectivity was
observed when an amino cinchonidine derivative (III) was used as the organocatalyst under the similar
reaction conditions. This demonstrated an example of activation of the nucelophilic component in the
desymmetrization of cyclic meso-anhydrides.
Keywords:
Desymmetrization
Organocatalysis
Michael addition
Thiourea
Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
reported by Oda.17 An enantioselective ring-opening of cyclic meso-
anhydrides yielded chemically differentiated carboxyl groups,
Over the past several decades, many efficient asymmetric pro-
tocols have been developed for synthesizing chiral nonracemic
substances through either metal-mediated1 or metal-free cataly-
sis.2 Catalytic asymmetric desymmetrization is a conventional
method that allows access to versatile enantioenriched chiral
building blocks without creating new stereogenic centers.3 Nu-
merous naturally occurring biologically active complex molecular
structures can be easily synthesized using these chiral products.4
Many functional prochiral and meso starting substrates have been
used in the simple symmetry-breaking operation, including olefinic
1,3-diol,5 3-substituted oxetane,6 epoxide,7 cyclohexadienone,8
cyclic ketone,9 cyclohexadiene,10 aziridine,11 1,3-dione,12 cyclohex-
anone,13 and bis(phenol).14 The use of a chiral Lewis acid catalysis in
enantioselective desymmetrization has been documented.15 By
contrast, organocatalysis is an alternative and environmentally
benign approach for performing desymmetrization reaction, which
possesses several synthetic advantages such as easy accessibility of
the starting substrates, creation of multiple stereogenic centers,
and the possibility of the final products undergoing additional
chemical transformations.16 The desymmetrization of anhydrides
catalyzed by a small organic molecule cinchona alkaloid was first
which are useful building blocks for numerous synthetic trans-
formations.18 The use of the privileged cinchona alkaloids and their
derivatives has pervaded a substantial part of organocatalysis.19
Many efficient synthetic methodologies have been developed us-
ing these bifunctional catalysts to activate both the nucleophilic
and electrophilic components synergistically.20 Therefore, we re-
port an enantioselective alcoholysis of cyclic meso-anhydrides with
primary nitroallylic alcohols to prepare both enantiomers of
hemiesters by using cinchonidine derived amino and thiourea
catalysts (Fig. 1).
* Corresponding author. Tel.: þ886 2 7734 6124; fax: þ886 2 2932 4249; e-mail
address: kchen@ntnu.edu.tw (K. Chen).
Fig. 1. Structures of various bifunctional organocatalysts IeV.
http://dx.doi.org/10.1016/j.tet.2014.10.008
0040-4020/Ó 2014 Elsevier Ltd. All rights reserved.

Y.m. Chen et al. / Tetrahedron 70 (2014) 9064e9069
9065
2. Results and discussion
Most enantioselective desymmetrization of cyclic meso-anhy-
drides involves using a simple alcohol in the presence of a catalyst.
The alcoholysis process requires the activation of the electrophilic
cyclic anhydrides followed by deprotonation of the alcoholic pro-
ton. The activation of the nucleophilic components has not been
extensively studied. The presence of a thiourea moiety in the cat-
alyst has been known to activate the nitro group in various enan-
tioselective reactions. Incorporating an auxiliary nitro group in the
nucleophilic alcohols might facilitate the desymmetrization of the
cyclic meso-anhydrides. To test this hypothesis, various cinchona
alkaloid based catalysts (IeV) were used in this study to catalyze
the asymmetric ring opening of meso-anhydrides. The primary
nitroallylic alcohol (2a) and cis-1,2-cyclohexene dicarboxylic an-
hydride (1a) were used as model substrates for the reaction at
ambient temperature. Both the chemical yield and enantiose-
lectivity were moderate when the thiourea catalyst I was used
(Table 1, entry 1). The use of catalyst II was able to improve the
reactivity and stereoselectivity (86% ee) in toluene (Table 1, entry
2). The corresponding hemiester 3a was obtained with stereo-
chemistry opposite to that observed when primary amino orga-
nocatalysts IIIeIV were used (Table 1, entries 3 and 4). Finally, using
a quinine catalyst to give the desired product with inferior results
(Table 1, entry 5).
Fig. 2. The structures of other hemisters 4aed when different allylic alcohols were
used catalyzed by II.
yield with moderate enantioselectivity (42% ee). The reaction of
racemic nitroallylic alcohol provided the desired hemiester 4d with
excellent enantioselectivity (93% ee).22 These data indicate that the
presence of a nitro group in allylic alcohols is essential in the cyclic
anhydride ring opening.
To determine whether any other solvents could be suitable for
this protocol, a survey of reaction media was conducted. We per-
formed the reaction in different solvents, including toluene, n-
pentane, benzene, and halogenated solvents in the presence of
catalyst II. Screening the solvents revealed that toluene was the
optimal solvent for the reaction (Table 2, entry 1). Both the re-
activity and selectivity were slightly decreased when benzene was
used (Table 2, entry 3). No reaction occurred when nonpolar n-
pentane was used (Table 2, entry 4). The desired product 3a was
obtained with high enantioselectivity (85% ee) in halogenated
solvents (Table 2, entries 5e7). The reactivity decreased consider-
ably when polar solvent, such as CH3CN were used (Table 2, entry
8). Surprisingly, an excellent chemical yield was obtained (96%)
when the amount of cyclic anhydride 1a was increased from 1.0 to
2.0 equiv with comparable enantioselectivity (Table 2, entry 9). The
enantioselectivity was further improved to 94% ee when the re-
action was performed at ꢀ20 ꢁC (Table 2, entry 10).
Table 1
Catalysts screening for the desymmetrization reaction of cis-1,2-cyclohexene di-
carboxylic anhydride (1a) with nitroallylic alcohol (2a)a
Table 2
Optimization of the desymmetrization reaction of cis-1,2-cyclohexene dicarboxylic
acid anhydride (1a) with nitroallylic alcohol (2a)a
Entry
Catalyst
t/h
Yield (%)b
ee (%)c
1
2
3
4
5
I
20
15
20
20
21
37
79
58
47
41
68
86
ꢀ61
ꢀ55
ꢀ31
II
III
IV
V
Entry
Solvent
t/h
Yield (%)b
ee (%)c
a
All reactions were carried out with cis-1,2-cyclohexene dicarboxylic acid an-
hydride 1a (1.0 equiv), nitroallylic alcohol 2a (1.0 equiv), and 10 mol % of organo-
catalysts (IeV) in toluene (0.8 mL) at ambient temperature.
1
2
3
4
5
6
7
8
Toluene
Mesitylene
Benzene
n-Pentane
CCl4
CHCl3
CH2Cl2
CH3CN
Toluene
Toluene
15
18
15
48
20
18
20
30
18
48
79
73
63
86
77
82
d
b
Isolated yield.
d
c
Determined by chiral HPLC analysis.
77
61
60
<10
96
76
85
81
d
The phenomenon of reversal of stereochemistry when thiourea
catalysts (I and II) and amino catalysts (III and IV) were used is
compelling. Presumably, the nitro group of the nucleophilic alcohol
was activated by the catalyst through hydrogen bond formation. To
confirm the hypothesis, we conducted 1H NMR studies on the in-
teraction between the nitroallylic alcohol 2a and the catalyst II in
deuterium toluene-d8. Examining the spectrum indicated the sig-
nals of methylene protons in nitroallylic alcohol 2a shifted slightly
9d
10e
84
94
88
a
All reactions were carried out with cis-1,2-cyclohexene dicarboxylic acid an-
hydride 1a (1.0 equiv), nitroallylic alcohol 2a (1.0 equiv), and 10 mol % of organo-
catalyst II in the solvent indicated (0.8 mL) at ambient temperature.
b
Isolated yield.
Determined by chiral HPLC analysis.
cis-1,2-Cyclohexene dicarboxylic acid anhydride:nitroallylic alcohol¼2:1 at
c
d
downfield from d (ppm) 4.16 (d) to 4.19 (s) while the olefinic proton
shifted upfield to 7.77 (s) from 7.79 (s).21 No changes in chemical
shifts were observed when cyclic meso-anhydride 1a and catalyst II
were mixed, potentially indicating the proximity between the nitro
group and the thiourea functionalities in the solution. Next, the use
of other allylic alcohols was investigated to verify the importance of
the nitro group in the desymmetrization reaction. Thus, we applied
the present protocol to other allylic alcohols as nucleophiles in the
presence of cinchonidine derived thiourea catalyst II. Using allylic
alcohol afforded the desired hemiester 4a with reasonable enan-
tioselectivity (Fig. 2). The reaction of cinnamyl alcohol resulted in
the expected product 4b in favorable chemical yield and moderate
enantioselectivity (58% ee). The use of 2-(hydroxymethyl)cyclohex-
2-enone produced the corresponding product in 64% chemical
ambient temperature.
e
cis-1,2-Cyclohexene dicarboxylic acid anhydride:nitroallylic alcohol¼2:1 at
ꢀ20 ꢁC.
After optimizing the reaction conditions, we evaluated the scope
of this methodology by using cis-1,2-cyclohexene dicarboxylic acid
anhydride 1a with various nitroallylic alcohols. The results were
summarized in Table 3. Various nitroallylic alcohols 2aei were in-
vestigated to establish the general utility of this asymmetric
transformation. Regardless of the substituent functionality and
orientation in the aromatic nucleus, the desymmetrization of ring
openings proceeded smoothly to give the desired products with
comparable results. Employing a 2-chloro substituted aryl group in

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Y.m. Chen et al. / Tetrahedron 70 (2014) 9064e9069
Table 3
with reasonable selectivity (81% ee) (Table 3, entry 9). The
desymmetrization products were characterized by IR, HRMS, 1H, 13
NMR spectroscopic data, and the absolute stereochemistry was
tentatively assigned by single crystal X-ray analysis of a represen-
tative product (1R,6S)-3b (Fig. 3).23
The reaction of various nitroallylic alcohols 2aei with cis-1,2-cyclohexene di-
C
carboxylic acid anhydride 1a mediated by catalyst IIa
Entry
1
Product
t/h
Yield (%)b
88
ee (%)c
94
48
2
3
72
72
81
77
99
91
Fig. 3. Thermal ellipsoid representation of 3b at 30% probability level.
To explore the scope of the asymmetric protocol further, we
examined the reaction between nitroallylic alcohol 2a and various
cyclic meso-anhydrides. As depicted in Fig. 4, the desymmetrization
reaction tolerated six-, five-, and three-membered cyclic anhy-
drides in the presence of catalyst II. Various anhydrides reacted
readily with nitroallylic alcohol 2a to provide the corresponding
hemiesters in high chemical yields with high levels of enantiose-
lectivity (3jel, 93e95% ee).
Preparing both enantiomeric products without resorting to the
antipodal catalyst is synthetically attractive. The use of the same
chirality of amino cinchonidine catalyst III (as to II) to obtain
a functionalized hemiester with opposite stereochemistry is of
worth noting (Table 1). Desymmetrization of various cyclic meso-
anhydrides with nitroallylic alcohol 2a in the presence of catalyst III
yields the enantiomeric hemiesters (Fig. 4, ent-3a, ent-3e, ent-3f,
and ent-3jel) with decreased stereoselectivity. The relative weak
interaction between the amino group and nitro functionality might
account for the low reactivity, which the reaction required to pro-
ceed at ambient temperature. Two working mechanisms that in-
volve general base catalysis17 and nucleophilic catalysis24 have
been proposed for the cyclic meso-anhydride ring opening.25
4
5
66
50
80
85
84
92
6
72
72
84
72
92
92
7
8
48
48
85
84
91
81
9
a
All reactions were carried out with cis-1,2-cyclohexene dicarboxylic acid an-
hydride 1a (2.0 equiv), nitroallylic alcohols 2aei (1.0 equiv), and 10 mol % of
organocatalyst II in toluene (0.8 mL) at ꢀ20 ꢁC.
b
Isolated yield.
Determined by chiral HPLC analysis.
c
the nucleophile yielded excellent enantioselectivity; however, the
stereoselectivity dropped when 3-chloro substituted substrate was
used (Table 3, entries 2 and 4). Comparable stereoselectivities were
observed when 4-substituent substrates was used (Table 3, entries
5e8). Using of 2-furyl substituted nitroallylic alcohol 2i provided 3i
Fig. 4. Examples of various nitroallylic alcohol 2a, 2e, and 2f react with different cyclic
anhydrides 1jel mediated by catalysts II and III, respectively.

Y.m. Chen et al. / Tetrahedron 70 (2014) 9064e9069
9067
Although the mechanism of the current work remains to be clari-
fied, a plausible reaction mode for the formation of hemiesters was
proposed. As illustrated in Fig. 5, hydrogen bonds were formed
between the thiourea moiety in organocatalyst II and the nitro
group in the nucleophile. The orientation of the six-membered
carbocycle in 1a toward the bicyclic skeleton in catalyst II might
cause steric repulsion. The formation of a desymmetrized product
(1R,6S) from the transition structure TS-II is energetically more
favorable than the structure of TS-I. The oxyanion that was gener-
ated was stabilized by the protonated tertiary amino group in
catalyst II.
indicated eluents. The enantiomeric excess value for a product was
determined by chiral-phase HPLC analysis.
4.2. Typical reaction procedure
To a solution of (E)-2-nitro-3-phenylprop-2-en-1-ol 2a (30 mg,
0.16 mmol) and 1-phenyl-3-((S)-quinolin-4-yl((1S,2S,4S,5R)-5-
vinylquinuclidin-2-yl)methyl)thiourea II (7.1 mg, 0.01 mmol) in
anhydrous toluene (0.80 mL) was added cyclic meso anhydride 1a
(50.8 mg, 0.33 mmol) in one portion at ꢀ20 ꢁC. The reaction mix-
ture was stirred at ꢀ20 ꢁC for the needed time period. The reaction
was monitored by TLC analysis and quenched with H2O (5 mL). The
mixture was extracted with CH2Cl2 (10 mL) and the organic layer
was dried over anhydrous Na2SO4, filtered, and concentrated in
vacuo. Purification by flash column chromatography (ethyl acetate/
hexanes¼1:3) afforded the desired adducts 3aei.
4.2.1. (1R,6S)-6-((((E)-2-Nitro-3-phenylallyl)oxy)carbonyl)cyclohex-
3-enecarboxylic acid (3a). Colorless oil. Yield: 88%; 1H NMR
(400 MHz, CDCl3):
3.10e3.16 (m, 2H), 5.17e5.25 (m, 2H), 5.70 (s, 2H), 7.42e7.48 (m, 5H),
8.34 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3):
d
¼2.35e2.42 (m, 2H), 2.56e2.62 (m, 2H),
Fig. 5. Plausible reaction mechanism.
d¼25.6, 25.6, 39.5,
39.6, 58.3, 125.0, 125.1, 129.3, 130.1, 130.91, 131.3, 140.2, 145.0, 172.4,
3. Conclusions
~
178.9 ppm; IR (CH2Cl2):
n
¼3030, 2977, 2954, 2926, 1736, 1702, 1527,
1447, 1329 cmꢀ1; HRMS (ESI-TOF): m/z calcd for C17H17NO6
[MþNa]þ 354.0954, found 354.0945; The ee value of 3a was 94%, tR
(minor)¼25.8 min, tR (major)¼27.0 min; HPLC analysis (Chiralcel OJ-
In conclusion, we demonstrated a practical desymmetrization
reaction catalyzed by using cinchona alkaloid derived thiourea
organocatalyst II. A wide range of nitroallylic alcohols 2aei were
used for the asymmetric ring opening of cyclic meso-anhydrides.
The products were obtained in high chemical yields (72e88%) with
high to excellent enantioselectivity (81e99% ee) under optimized
reaction conditions. The activation of the nitro group in the nu-
cleophilic alcohols by the thiourea moiety is essential. In particular,
activation of the nitroallylic alcohols with the amino catalyst (III)
yields enantiomeric hemiesters with reasonable to high stereo-
selectivity (68e87% ee). The use of cinchona alkaloids and their
derivatives as catalysts in organocatalytic reactions is currently
under investigation.
H,
l
¼254 nm, 10% iPrOH/hexanes, flow rate¼1.0 mL/min).
4.2.2. (1R,6S)-6-((((E)-3-(2-Chlorophenyl)-2-nitroallyl)oxy)car-
bonyl)cyclohex-3-enecarboxylic acid (3b). Greenish solid. Yield: 81%;
mp 68.5e69.9 ꢁC; 1H NMR (400 MHz, CDCl3):
d¼2.37e2.41 (m, 2H),
2.55e2.60 (m, 2H), 3.05e3.22 (m, 2H), 5.09e5.11 (m, 2H), 5.69 (s, 2H),
7.26e7.35 (m, 2H), 7.40e7.49 (m, 2H), 8.47 (s, 1H) ppm; 13C NMR
(100 MHz, CDCl3):
d
¼25.5, 39.3, 39.6, 58.0, 124.9, 125.0, 127.5, 129.8,
130.0, 130.3, 132.1, 135.1, 137.0, 146.2, 172.2, 179.7 ppm; IR (CH2Cl2):
¼3022, 2923, 2839, 1740, 1706, 1527, 1436, 1340 cmꢀ1; HRMS (ESI-
~
n
TOF): m/z calcd for C17H16ClNO6 [MþNa]þ 388.0564, found 388.0564;
[Mþ2þNa]þ 390.0534, found 390.0578; The ee valueof 3b was 99%, tR
(major)¼49.1 min, tR (minor)¼58.0 min; HPLC analysis (Chiralcel OJ-
4. Experimental
H,
l
¼254 nm, 7% iPrOH/hexanes, flow rate¼0.5 mL/min).
4.1. General remarks
4.2.3. Crystal structure data of 3b at 200 K. C17H16ClNO6,
Chemicals and solvents were purchased from commercial sup-
pliers and used as received. The cyclic meso-anhydrides were pur-
chased from SigmaeAldrich and used as received. IR spectra were
recorded with a PerkineElmer 500 spectrometer. 1H and 13C NMR
spectra were recorded on a Bruker Avance 400 (400 MHz), Bruker
Avance 500 (500 MHz), and Bruker Avance III HD 600 (600 MHz)
spectrometer. Chemical shifts were reported in parts per million
(ppm), and the residual solvent peak was used as an internal refer-
M¼365.76 g molꢀ1; tetragonal, point group I 41/a, bond precision:
ꢀ
CeC¼0.0099 A, a¼26.779(13), b¼26.779(13), c¼9.116(4),
a¼90,
3
ꢀ
ꢀ
b
¼90,
g
¼90, V¼6537(5) A , F(000)¼3040,
l
(Mo-K
a
)¼0.71073 A,
D¼1.487 cmꢀ3
,
Nref¼2872,
R
(reflections)¼0.0836(1076), wR2
(reflections)¼0.2096(2872) for all data.
4.2.4. (1R,6S)-6-((((E)-3-(3-Methoxyphenyl)-2-nitroallyl)oxy)car-
bonyl)cyclohex-3-enecarboxylic acid (3c). Colorless oil. Yield: 77%;
ence: proton (TMS,
d
d
0.00), carbon (CDCl3,
4.87), carbon (MeOH-d4, 49.1); proton (DMSO-d6,
39.5). Multiplicity is indicated as follows: s (singlet),
d
77.0); proton (MeOH-d4,
1H NMR (400 MHz, MeOD):
d
¼2.27e2.32 (m, 2H), 2.44e2.51 (m,
d
d
2.50), carbon
2H), 2.97e3.24 (m, 2H), 3.76 (s, 3H), 5.10e5.16 (m, 2H), 5.59 (s, 2H),
(DMSO-d6,
d
6.99e7.06 (m, 3H), 7.33 (t, J¼8.0 Hz, 1H), 8.29 (s, 1H) ppm; 13C NMR
d (doublet), t (triplet), q (quartet), m (multiple), dd (doublet of
doublet), br. s (broad singlet). Coupling constants were reported in
Hertz (Hz). All high resolution mass spectra were obtained with
a JEOL, JMS-700, Japan or Waters, LCT, UK spectrometer. The X-ray
diffraction measurements were carried out at 200 K with a KAPPA
(100 MHz, MeOD):
126.1, 126.6, 131.5, 134.0, 141.0, 147.0, 161.7, 174.6, 176.9 ppm; IR
d
¼27.0, 27.1, 40.9, 56.2, 59.4, 116.2, 118.5, 123.8,
~
(CH2Cl2):
n
¼2916, 2854, 1733, 1706, 1691, 1600, 1523, 1451,
1451 cmꢀ1; HRMS (ESI-TOF): m/z calcd for C18H19NO7 [M]þ
361.1162, found 361.1164; The ee value of 3c was 91%, tR (minor)¼
40.6 min, tR (major)¼43.2; HPLC analysis (Chiralcel OJ-H,
APEX II CCD area detector system equipped with a graphite mono-
chromator and a Mo-K
a
fine-focus sealed tube (k¼0.71073 A). Merck
l
¼254 nm, 10% iPrOH/hexanes, flow rate¼1.0 mL/min).
ꢀ
precoated TLC plates (Merck 60 F254) were used for thin layer
chromatography, and compounds were visualized under UV light at
254 nm. Solutions were evaporated to dryness under reduced pres-
sure with a rotary evaporator, and the residues were purified by flash
column chromatography on silica gel (230e400 mesh) with the
4.2.5. (1R,6S)-6-((((E)-3-(3-Chlorophenyl)-2-nitroallyl)oxy)car-
bonyl)cyclohex-3-enecarboxylic acid (3d). Colorless oil. Yield: 80%;
1H NMR (400 MHz, MeOD):
2H), 3.07e3.31 (m, 2H), 5.16e5.22 (m, 2H), 5.67 (s, 2H), 7.48e7.51
d
¼2.33e2.39 (m, 2H), 2.40e2.58 (m,

9068
Y.m. Chen et al. / Tetrahedron 70 (2014) 9064e9069
(m, 3H), 7.51e7.60 (m, 1H), 8.35 (s, 1H) ppm; 13C NMR (100 MHz,
MeOD):
131.9, 132.1, 134.8, 136.3, 139.3, 148.0, 174.4, 176.9 ppm; IR (CH2Cl2):
3.00e3.09 (m, 1H), 3.30e3.31 (m, 1H), 5.40e5.53 (m, 2H), 5.62 (s,
2H), 6.70 (t, J¼2.0 Hz, 1H), 7.17 (d, J¼3.2 Hz, 1H), 7.86 (d, J¼1.2 Hz,
d
¼26.9, 27.13, 40.9, 41.0, 59.1, 126.1, 126.6, 129.5, 131.2,
1H), 8.12 (s, 1H) ppm; 13C NMR (100 MHz, MeOD):
d¼27.0, 27.0,
n
¼3330, 2938, 2908, 1706, 1649, 1558, 1527, 1337 cmꢀ1; HRMS (ESI-
40.9, 59.5, 114.6, 124.0, 126.0, 126.3, 126.5, 142.7, 148.4, 150.0, 174.8,
~
17H16ClNO6 [MþNa]þ 388.0564, found
176.9 ppm; IR (CH2Cl2):
n
¼3439, 2923, 2865, 1733, 1699, 1647, 1512,
~
TOF): m/z calcd for
C
388.0569; [Mþ2þNa]þ 390.0534, found 390.0576; The ee value of
3d was 84%, tR (minor)¼31.1 min, tR (major)¼37.1 min; HPLC
1436 cmꢀ1; HRMS (ESI-TOF): m/z calcd for C15H15NO6 [MþNa]þ
344.0746, found 344.0749; The ee value of 3i was 81%, tR (major)¼
33.5 min, tR (minor)¼38.6 min; HPLC analysis (Chiralcel AD-H,
analysis (Chiralcel AD-H,
rate¼1.0 mL/min).
l
¼254 nm, 10% iPrOH/hexanes, flow
l
¼254 nm, 10% iPrOH/hexanes, flow rate¼1.0 mL/min).
4.2.6. (1R,6S)-6-((((E)-3-(4-Methoxyphenyl)-2-nitroallyl)oxy)car-
bonyl)cyclohex-3-enecarboxylic acid (3e). Colorless oil. Yield: 85%;
4.2.11. (1R,2S)-2-((((E)-2-Nitro-3-phenylallyl)oxy)carbonyl)cyclo-
hexanecarboxylic acid (3j). Colorless oil. Yield: 90%; 1H NMR
1H NMR (400 MHz, DMSO):
d
¼2.25e2.34 (m, 2H), 2.36e2.50 (m, 2H),
(400 MHz, MeOD):
d
¼1.41e1.54 (m, 4H), 1.74e1.85 (m, 2H),
2.99e3.05 (m, 2H), 3.82 (s, 3H), 5.07e5.19 (m, 2H), 5.61 (s, 2H), 7.07 (d,
1.93e2.08 (m, 2H), 2.86e2.92 (m, 2H), 5.14 (d, J¼13.2 Hz, 1H), 5.25
J¼8.4 Hz, 2H), 7.59 (d, J¼8.4 Hz, 2H), 8.38 (s, 1H) ppm; 13C NMR
(d, J¼12.8 Hz, 1H), 7.49e7.58 (m, 5H), 8.40 (s, 1H) ppm; 13C NMR
(100 MHz, DMSO):
d
¼25.8, 26.4, 56.2, 58.9, 115.5, 123.7, 125.5, 126.0,
(100 MHz, MeOD):
d
¼23.4, 23.5, 25.7, 26.2, 42.2, 42.3, 57.7, 128.9,
~
133.7,140.7, 143.4,162.8,173.4, 175.0 ppm; IR (CH2Cl2):
n
¼3434, 2257,
130.0, 130.8, 131.2, 139.5, 145.4, 173.5, 175.7 ppm; IR (CH2Cl2):
2129,1737,1654,1603,1523,1508 cmꢀ1;HRMS(ESI-TOF):m/zcalcd for
n
¼2938, 2862, 1736, 1702, 1655, 1599, 1526, 1451 cmꢀ1; HRMS (ESI-
~
C
18H19NO7 [MꢀH]ꢀ 360.1084, found 360.1092; The ee value of 3e was
TOF): m/z calcd for C17H19NO6 [MþNa]þ 356.1110, found 356.1100;
91%, tR (minor)¼40.5 min, tR (major)¼46.0; HPLC analysis (Chiralcel
The ee value of 3j was 93%, tR (major)¼23.1 min, tR (minor)¼
i
OJ-H,
l
¼254 nm, 10% iPrOH/hexanes, flow rate¼1.0 mL/min).
27.1 min; HPLC analysis (Chiralcel AD-H,
l
¼254 nm, 10% PrOH/
hexanes, flow rate¼1.0 mL/min).
4.2.7. (1R,6S)-6-((((E)-3-(4-Bromophenyl)-2-nitroallyl)oxy)car-
bonyl)cyclohex-3-enecarboxylic acid (3f). Colorless oil. Yield: 84%;
4.2.12. (1R,2S)-2-((((E)-2-Nitro-3-phenylallyl)oxy)carbonyl)cyclo-
1H NMR (400 MHz, MeOD):
d
¼2.34e2.39 (m, 2H), 2.40e2.58 (m,
pentanecarboxylic acid (3k). Colorless oil. Yield: 67%; 1H NMR
2H), 3.08e3.31 (m, 2H), 5.14e5.23 (m, 2H), 5.67 (s, 2H), 7.48 (d,
J¼8.4 Hz, 2H), 7.68 (d, J¼6.4 Hz, 2H), 8.36 (s, 1H) ppm; 13C NMR
(400 MHz, MeOD):
d
¼1.63e1.74 (m, 1H), 1.79e1.99 (m, 1H),
2.00e2.05 (m, 4H), 3.11e3.15 (m, 2H), 5.12 (d, J¼12.8 Hz, 1H), 5.27
(100 MHz, MeOD):
d
¼26.7, 27.3, 40.9, 41.0, 59.3, 126.1, 126.5, 126.9,
(d, J¼13.2 Hz, 1H), 7.50e7.51 (m, 2H), 7.52e7.59 (m, 3H), 8.40 (s, 1H)
131.9, 133.2, 133.7, 139.9, 147.3, 174.6, 177.0 ppm; IR (CH2Cl2):
ppm; 13C NMR (100 MHz, MeOD):
d¼23.2, 28.1, 28.7, 46.3, 57.7, 78.1,
~
n
¼3434, 3030, 2977, 2923, 2826, 1738, 1706, 1655, 1587, 1529,
128.9, 130.1, 130.8, 131.2, 139.5, 145.4, 173.8, 176.2 ppm; IR (CH2Cl2):
1409 cmꢀ1; HRMS (ESI-TOF): m/z calcd for C17H16BrNO6 [MþNa]þ
432.0059, found 432.0052; [Mþ2þNa]þ 434.0038, found
434.0023; The ee value of 3f was 92%, tR (minor)¼31.7 min, tR
n
¼3431, 2969, 2877, 2648, 2549, 1739, 1702, 1649, 1527 cm
;
ꢀ1
~
HRMS (ESI-TOF): m/z calcd for C16H17NO6 [MþNa]þ 342.0954,
found 342.0947; The ee value of 3k was 95%, tR (major)¼28.0 min,
(major)¼36.9 min; HPLC analysis (Chiralcel OJ-H,
l¼254 nm, 10%
tR (minor)¼29.2 min; HPLC analysis (Chiralcel AD-H,
10% iPrOH/hexanes, flow rate¼1.0 mL/min).
l¼254 nm,
iPrOH/hexanes, flow rate¼1.0 mL/min).
4.2.8. (1R,6S)-6-((((E)-2-Nitro-3-(p-tolyl)allyl)oxy)carbonyl)cyclo-
4.2.13. (1S,3R)-2,2-Dimethyl-3-((((E)-2-nitro-3-phenylallyl)oxy)car-
hex-3-enecarboxylic acid (3g). Colorless oil. Yield: 72%; 1H NMR
bonyl)cyclopropanecarboxylic acid (3l). Colorless oil. Yield: 56%; 1H
(400 MHz, MeOD):
d
¼2.33e2.36 (m, 2H), 2.40 (s, 3H), 2.51e2.60 (m,
NMR (400 MHz, MeOD):
d
¼1.23 (s, 3H), 1.41 (s, 3H), 1.98e2.05 (m,
2H), 3.08e3.31 (m, 2H), 5.17e5.26 (m, 2H), 5.67 (s, 2H), 7.33 (d,
J¼8.0 Hz, 2H), 7.46 (d, J¼8.0 Hz, 2H), 8.38 (s, 1H) ppm; 13C NMR
2H), 5.11 (d, J¼13.2 Hz, 1H), 5.31 (d, J¼13.2 Hz, 1H), 7.50e7.51 (m,
3H), 7.58e7.60 (m, 2H), 8.40 (s, 1H) ppm; 13C NMR (100 MHz,
(125 MHz, MeOD):
d
¼21.7, 26.8, 27.2, 40.8, 40.9, 59.6, 126.1, 126.5,
MeOD):
d
¼14.6, 25.7, 26.5, 31.2, 31.8, 57.9, 128.9, 130.1, 130.8, 131.2,
~
129.8, 131.1, 131.8, 141.3, 143.6, 145.9, 174.6, 176.8 ppm; IR (CH2Cl2):
139.5, 168.8, 171.2 ppm; IR (CH2Cl2):
n
¼3062, 3027, 2964, 2928,
~
n
¼3424, 2961, 2862, 2076, 1729, 1653, 1638, 1527, 1512 cmꢀ1; HRMS
2744, 2679, 1783, 1743, 1704, 1654, 1600, 1576, 1526 cmꢀ1; HRMS
(ESI-TOF): m/z calcd for C16H17NO6 [MþNa]þ 342.0954, found
342.0955; The ee value of 3l was 93%, tR (minor)¼21.6 min, tR
(ESI-TOF): m/z calcd for C18H19NO6 [MþNa]þ 368.1110, found
368.1108; The ee value of 3g was 92%, tR (minor)¼17.5 min, tR
(major)¼18.9 min; HPLC analysis (Chiralcel OJ-H,
iPrOH/hexanes, flow rate¼1.0 mL/min).
l¼254 nm, 10%
(major)¼23.0 min; HPLC analysis (Chiralcel AD-H,
l¼254 nm, 10%
iPrOH/hexanes, flow rate¼1.0 mL/min).
4.2.9. (1R,6S)-6-((((E)-3-(4-Fluorophenyl)-2-nitroallyl)oxy)carbonyl)
4.2.14. (1R,6S)-6-((Allyloxy)carbonyl)cyclohex-3-enecarboxylic acid
cyclohex-3-enecarboxylic acid (3h). Colorless oil. Yield: 85%; 1H
(4a). Colorless oil. Yield: 91%; 1H NMR (400 MHz, CDCl3):
NMR (400 MHz, MeOD):
d
¼2.34e2.40 (m, 2H), 2.41e2.59 (m, 2H),
d
¼2.34e2.40 (m, 2H), 2.55e2.64 (m, 2H), 3.08e3.10 (m, 2H),
3.10e3.31 (m, 2H), 5.16e5.24 (m, 2H), 5.67 (s, 2H), 7.25 (t, J¼8.8 Hz,
4.56e4.65 (s, 2H), 5.20e5.33 (m, 2H), 5.66e5.69 (m, 2H), 5.72e5.94
2H), 7.61e7.65 (m, 2H), 8.40 (s, 1H) ppm; 13C NMR (150 MHz,
(m, 1H) ppm; 13C NMR (100 MHz, CDCl3):
d
¼25.6, 25.8, 39.5, 39.6,
~
MeOD):
d
¼25.2, 25.7, 39.3, 39.4, 57.8, 116.0, 124.6, 125.0, 127.6,
65.4,118.1,125.1,125.1,132.0,172.9,178.3 ppm; IR (CH2Cl2):
n
¼3445,
132.7, 138.5, 145.1, 164.4, 173.1, 175.4 ppm; 19F NMR (564 MHz,
3031, 2641, 1731, 1713, 1421 cmꢀ1; HRMS (ESI-TOF): m/z calcd for
MeOD):
d
¼ꢀ111.14 ppm; IR (CH2Cl2):
n
¼3434, 3030, 2961, 2908,
C
11H14O4 [MþNa]þ 233.0790 found 233.0786; The ee value of 4awas
~
2854, 2083, 1737, 1702, 1654, 1603, 1528, 1508 cmꢀ1; HRMS (ESI-
68%, tR (minor)¼16.4 min, tR (major)¼20.2; HPLC analysis (Chiralcel
TOF): m/z calcd for
C
17H16FNO6 [MþNa]þ 372.0859, found
AS-H,
l
¼220 nm, 10% iPrOH/hexanes, flow rate¼0.5 mL/min).
372.0861; The ee value of 3h was 91%, tR (minor)¼32.4 min, tR
(major)¼34.3; HPLC analysis (Chiralcel OJ-H,
hexanes, flow rate¼1.0 mL/min).
l
¼254 nm, 10% iPrOH/
4.2.15. (1R,6S)-6-((Cinnamyloxy)carbonyl)cyclohex-3-enecarboxylic
acid (4b). Colorless oil. Yield: 77%; 1H NMR (400 MHz, MeOD):
d
¼2.23e2.40 (m, 2H), 2.54e2.60 (m, 2H), 3.08e3.11 (m, 2H),
4.2.10. (1R,6S)-6-((((E)-3-(Furan-2-yl)-2-nitroallyl)oxy)carbonyl)cy-
4.73e4.75 (dd, J¼6.0, 1.2 Hz, 2H), 5.67 (s, 2H), 6.26 (d, J¼12.0 Hz,
clohex-3-enecarboxylic acid (3i). Colorless oil. Yield: 84%; 1H NMR
1H), 6.27e6.34 (m, 1H), 7.21e7.23 (m, 2H), 7.25e7.28 (m, 1H),
(400 MHz, MeOD):
d¼2.29e2.36 (m, 2H), 2.47e2.54 (m, 2H),
7.30e7.42 (m, 2H) ppm; 13C NMR (100 MHz, MeOD):
d¼27.0, 27.2,

Y.m. Chen et al. / Tetrahedron 70 (2014) 9064e9069
9069
Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I., Ed.; Wiley-VCH: New York,
NY, 2000.
40.9, 41.1, 66.3, 124.6, 126.3, 126.5, 127.8, 129.1, 129.8, 134.8, 138.1,
~
175.2,177.2 ppm; IR (CH2Cl2):
n
¼3029, 2921, 2854, 2349,1861,1842,
2. (a) Enantioselective Organocatalyzed Reactions; Mahrwald, R., Ed.; Springer:
Berlin, Germany, 2011; (b) Pellissier, H. Recent Developments in Asymmetric
Organocatalysis; RSC: Cambridge, UK, 2010, Vols. I and II; (c) Enantioselective
Organocatalysis: Reactions and Experimental Procedures; Dalko, P. I., Ed.; Wiley-
VCH: Weinheim, Germany, 2007; For recent reviews on organocatalytic pro-
cesses, see: (d) Moyano, A.; Rios, R. Chem. Rev. 2011, 111, 4703; (e) Graaff, C.;
Ruijter, E.; Orru, R. V. A. Chem. Soc. Rev. 2012, 41, 3969; (f) Pellissier, H. Adv.
Synth. Catal. 2012, 354, 237; (g) Jensen, K. L.; Dickmeiss, G.; Jiang, H.; Albrecht,
q.; Jørgensen, K. A. Acc. Chem. Res. 2012, 45, 248.
3. For review articles, see: (a) Diaz-de-Villegas, M. D.; Galvez, J. A.; Badorrey, R.;
Lopez-Ram-de-Viu, M. P. Chem.dEur. J. 2012, 18, 13920; (b) Enriquez-Garcia, A.;
Kundig, E. P. Chem. Soc. Rev. 2012, 41, 7803; (c) Rodriguez-Docampo, Z.; Connon,
S. J. ChemCatChem 2012, 4, 151; (d) Diaz-de-Villegas, M. D.; Galvez, J. A.; Etayo,
P.; Badorrey, R.; Lopez-Ram-de-Viu, M. P. Chem. Soc. Rev. 2011, 40, 5564; (e)
Atodiresei, I.; Schiffers, I.; Bolm, C. Chem. Rev. 2007, 107, 5683; (f) Chen, Y.;
McDaid, P.; Deng, L. Chem. Rev. 2003, 103, 2965; (g) Spivey, A. C.; Andrews, B. I.
Angew. Chem., Int. Ed. 2001, 40, 3131.
1777, 1729, 1708 cmꢀ1; HRMS (ESI-TOF): m/z calcd for C17H18O4
[MꢀH]- 285.1127, found 285.1124; The ee value of 4b was 58%, tR
(minor)¼15.2 min, tR (major)¼16.6 min; HPLC analysis (Chiralcel
i
AD-H,
l
¼254 nm, 10% PrOH/hexanes, flow rate¼1.0 mL/min).
4.2.16. (1R,6S)-6-(((6-Oxocyclohex-1-en-1-yl)methoxy)carbonyl)cy-
clohex-3-enecarboxylic acid (4c). Colorless oil. Yield: 64%; 1H NMR
(400 MHz, CDCl3):
d
¼1.99e2.04 (m, 2H), 2.32e2.48 (m, 6H),
2.53e2.61 (m, 2H), 3.06e3.08 (m, 2H), 4.77e4.78 (m, 2H), 5.68 (s,
2H), 7.00 (t, J¼4.0 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3):
¼22.6,
d
25.6, 25.7, 38.0, 39.3, 39.5, 39.6, 61.6, 125.0,125.1, 134.3, 148.6, 172.8,
~
178.6,198.1 ppm; IR (CH2Cl2):
n
¼3420, 3037, 2918, 2852,1772,1736,
1717, 1697, 1646, 1636, 1559, 1539 cmꢀ1; HRMS (ESI-TOF): m/z calcd
for C15H18O5 [MþNa]þ 301.1052, found 301.1044; The ee value of 4c
was 42%, tR (minor)¼19.1 min, tR (major)¼21.8 min; HPLC analysis
4. (a) Nicolas, J.; Mura, S.; Brambilla, D.; Mackiewicz, N.; Couvreur, P. Chem. Soc.
ꢁ
Rev. 2013, 42, 1147; (b) Fogarty, A. C.; Duboue-Dijon, E.; Sterpone, F.; Hynes, J. T.;
Laage, D. Chem. Soc. Rev. 2013, 42, 5672; (c) Evans, A. C.; Longbottom, D. A.;
ꢂ
Matsuoka, M.; Davies, J. E.; Turner, R.; Franckevicius, V.; Ley, S. V. Org. Biomol.
(Chiralcel AD-H,
min).
l
¼254 nm, 10% iPrOH/hexanes, flow rate¼1.0 mL/
Chem. 2009, 7, 747; (d) Anstiss, M.; Nelson, A. Org. Biomol. Chem. 2006, 4, 4135.
5. Ke, Z.; Tan, C. K.; Chen, F.; Yeung, Y.-Y. J. Am. Chem. Soc. 2014, 136, 5627.
6. Wang, Z.; Chen, Z.; Sun, J. Angew. Chem., Int. Ed. 2013, 52, 6685.
7. Wang, Z.; Law, W. K.; Sun, J. Org. Lett. 2013, 15, 5964.
8. Jia, M.-Q.; Liu, C.; You, S.-L. J. Org. Chem. 2012, 77, 10996.
9. (a) Zhou, L.; Liu, X.; Ji, J.; Zhang, Y.; Hu, X.; Lin, L.; Feng, X. J. Am. Chem. Soc. 2012,
4.2.17. (1R,6S)-6-((((S,E)-1-Ethoxy-3-nitro-1-oxo-4-phenylbut-3-en-
2-yl)oxy)carbonyl)cyclohex-3-enecarboxylic acid (4d). Colorless oil.
Yield: 48%; 1H NMR (400 MHz, MeOD):
2.37e2.38 (m, 2H), 2.42e2.66 (m, 2H), 3.08e3.11 (m, 1H), 3.18e3.31
(m, 1H), 4.15e4.21 (m, 2H), 5.61e5.70 (m, 2H), 6.52 (s, 1H),
7.47e7.53 (m, 5H), 8.50 (s, 1H) ppm; 13C NMR (100 MHz, MeOD):
d
¼1.20 (t, J¼7.2 Hz, 3H),
134, 17023; (b) Dickmeiss, G.; De Sio, V.; Udmark, J.; Poulsen, T. B.; Marcos, V.;
ꢁ
Jørgensen, K. A. Angew. Chem., Int. Ed. 2009, 48, 6650; (c) Companyo, X.; Valero,
G.; Crovetto, L.; Moyano, A.; Rios, R. Chem.dEur. J. 2009, 15, 6564.
10. Ikeuchi, K.; Ido, S.; Yoshimura, S.; Asakawa, T.; Inai, M.; Hamashima, Y.; Kan, T.
Org. Lett. 2012, 14, 6016.
11. Sala, G. D.; Lattanzi, A. Org. Lett. 2009, 11, 3330.
12. Mori, K.; Katoh, T.; Suzuki, T.; Noji, T.; Yamanaka, M.; Akiyama, T. Angew. Chem.,
Int. Ed. 2009, 48, 9652.
d
¼14.4, 26.9, 27.2, 40.8, 40.9, 63.7, 67.4, 126.1, 126.7, 130.5, 131.2,
131.2, 132.6, 142.3, 146.4, 167.6, 173.5, 176.7 ppm; IR (CH2Cl2):
n
¼3431, 3055, 3033, 2590, 2059,1767,1738, 1705,1653 cmꢀ1; HRMS
~
13. Ramachary, D. B.; Barbas, C. F., III. Org. Lett. 2005, 7, 1577.
(ESI-TOF): m/z calcd for C20H21NO8 [MþNa]þ, 426.1165, found
14. Lewis, C. A.; Gustafson, J. L.; Chiu, A.; Balsells, J.; Pollard, D.; Murry, J.; Reamer,
R. A.; Hansen, K. B.; Miller, S. J. J. Am. Chem. Soc. 2008, 130, 16358.
15. (a) Roux, C.; Candy, M.; Pons, J.-M.; Chuzel, O.; Bressy, C. Angew. Chem., Int. Ed.
2014, 53, 766; (b) Yoshida, M.; Sassa, N.; Kato, T.; Fujinami, S.; Soeta, T.; In-
omata, K.; Ukaji, Y. Chem.dEur. J. 2014, 20, 2058; (c) Babij, N. R.; Wolfe, J. P.
Angew. Chem., Int. Ed. 2013, 52, 9247; (d) Liu, K.; Teng, H.-L.; Yao, L.; Tao, H.-Y.;
Wang, C.-J. Org. Lett. 2013, 15, 2250; (e) Hayashi, M.; Shiomi, N.; Funahashi, Y.;
Nakamura, S. J. Am. Chem. Soc. 2012, 134, 19366; (f) Lee, J. Y.; You, Y. S.; Kang, S.
H. J. Am. Chem. Soc. 2011, 133, 1772; (g) Gopinath, P.; Watanabe, T.; Shibasaki, M.
Org. Lett. 2012, 14, 1358; (h) Piarulli, U.; Daubos, P.; Claverie, C.; Roux, M.;
Gennari, C. Angew. Chem., Int. Ed. 2003, 42, 234; (i) Shintani, R.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 1057; (j) Seebach, D.; Jaeschke, G.; Wang, Y. M. Angew.
Chem., Int. Ed. Engl. 1995, 34, 2395.
426.1171; The ee value of 4d was 93%, tR (major)¼18.9 min, tR
(minor)¼34.8 min; HPLC analysis (Chiralcel AD-H,
iPrOH/hexanes, flow rate¼1.0 mL/min).
l¼254 nm, 10%
4.3. General procedure for the synthesis of enantiomeric
products ent-3
To a solution of meso-anhydride 1a (50.8 mg, 0.33 mmol) in
anhydrous toluene (0.80 mL) was sequentially added (E)-2-nitro-3-
phenylprop-2-en-1-ol 2a (30 mg, 0.16 mmol) and (S)-quinolin-4-
yl((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methanamine III (4.9 mg,
0.01 mmol). The reaction vial was then capped, and the reaction
mixture was stirred at ambient temperature for 24 h. The reaction
was quenched with H2O (5 mL) and extracted with EtOAc (10 mL).
The organic layer was separated and dried over anhydrous Na2SO4,
filtered, and concentrated in vacuo. Purification by flash column
chromatography (ethyl acetate/hexanes¼1:3) afforded the desired
ent-products: ent-3a, ent-3e, ent-3f, and ent-3jel.
ꢁ
ꢁ
ꢁ~
16. Fernandez-Perez, H.; Etayo, P.; Lao, J. R.; Nunez-Rico, J. L.; Vidal-Ferran, A. Chem.
Commun. 2013, 10666.
17. (a) Hiratake, J.; Yamamoto, Y.; Oda, J. J. Chem. Soc., Chem. Commun. 1985, 1717;
(b) Hiratake, J.; Inagaki, M.; Yamamoto, Y.; Oda, J. J. Chem. Soc., Perkin Trans. 1
1987, 1053.
18. (a) Schmitt, E.; Schiffers, I.; Bolm, C. Tetrahedron 2010, 6349; (b) Manzano, R.;
ꢁ
ꢁ
Andres, J. M.; Muruzabal, M.-D.; Pedrosa, R. J. Org. Chem. 2010, 75, 5417; (c) Li,
H.; Liu, X.; Wu, F.; Tang, L.; Deng, L. Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 20625;
(d) Peschiulli, A.; Gun’ko, Y.; Connon, S. J. J. Org. Chem. 2008, 73, 2454; (e) Oh, S.
H.; Rho, H. S.; Lee, J. W.; Lee, J. E.; Youk, S. H.; Chin, J.; Song, C. E. Angew. Chem.,
Int. Ed. 2008, 47, 7872; (f) Peschiulli, A.; Quigley, C.; Tallon, S.; Gun’ko, Y. K.;
Connon, S. J. J. Org. Chem. 2008, 73, 6409; (g) Bolm, C.; Schiffers, I.; Dinter, C. L.;
Gerlach, A. J. Org. Chem. 2000, 65, 6984; (h) Chen, Y.; Tian, S.-K.; Deng, L. J. Am.
Chem. Soc. 2000, 122, 9542.
Acknowledgements
19. Song, C. E. In Cinchona Alkaloids in Synthesis & Catalysis: Ligands, Immobilization
and Organocatalysis; Wiley-VCH: Weinheim, Germany, 2009.
20. For review articles, see: (a) Yeboah, E. M. O.; Yeboah, S. O.; Singh, G. S. Tetra-
hedron 2011, 67, 1725; (b) Connon, S. J. Chem. Commun. 2008, 2499; (c) Tian, S.-
K.; Chen, Y.; Hang, J.; Tang, L.; McDaid, P.; Deng, L. Acc. Chem. Res. 2004, 37, 621
For recent selected examples, see: (d) Singh, R. P.; Bartelson, K.; Wang, Y.; Su,
H.; Lu, X.; Deng, L. J. Am. Chem. Soc. 2008, 130, 2422; (e) McCooey, S. H.; Connon,
S. J. Angew. Chem., Int. Ed. 2005, 44, 6367.
We thank the Ministry of Science and Technology of the Re-
public of China (MOST 102-2113-M-003-005-MY3) for its financial
support of this work.
Supplementary data
21. See Supplementary data for 1H NMR dilution experiments.
22. The organocatalytic kinetic resolution of racemic secondary nitroallylic alco-
hols with simultaneous desymmetrization of prochiral cyclic anhydrides was
investigated in our laboratory.
23. The supplementary crystallographic data of 3b (CCDC-979353) can be obtained
free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif.
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2014.10.008.
References and notes
24. Aitken, R. A.; Gopal, J.; Hirst, J. A. J. Chem. Soc., Chem. Commun. 1988, 632.
25. Dedeoglu, B.; Catak, S.; Houk, K. N.; Aviyente, V. ChemCatChem 2010, 2, 1122.
1. (a) Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals,
2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, Germany, 2004; (b)