Highly enantioselective Michael reaction employing cycloheptanone and cyclooctanone as nucleophiles

Article abstract of DOI:10.1039/c4nj01206b

An organocatalytic Michael reaction of cycloheptanone and cyclooctanone with nitrodienes and nitroolefins catalyzed by a hydroquinine-based primary amine catalyst has been accomplished. The corresponding Michael adducts were obtained in good yields (up to

Full text of DOI:10.1039/c4nj01206b

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DOI: 10.1039/C4NJ01206B
An organocatalytic Michael reaction of cycloheptanone and cyclooctanone with nitrodienes and
nitroolefins catalyzed by primary amine catalysts has been accomplished.

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DOI: 10.1039/C4NJ01206B
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PAPER
Highly Enantioselective Michael Reaction Employing
Cycloheptanone and Cyclooctanone as Nucleophiles
Cite this: DOI: 10.1039/c3nj00000x
Ai-Bao Xia,a Long Zhao,a Tao Wang,a Yan-Peng Zhang,a Ai-Guo Zhong,b Dan-Qian
Xua,* and Zhen-Yuan Xua,*
Received 00th XXXXX 2013,
Accepted 00th XXXXX 2013
An organocatalytic Michael reaction of cycloheptanone and cyclooctanone with nitrodienes
and nitroolefins catalyzed by a hydroquinine-based primary amine catalyst has been
accomplished. The corresponding Michael adducts were obtained in good yields (up to 88%)
with good to excellent diastereoselectivities (up to >100:1) and enantioselectivities (up to
>99% ee). The absolute configuration of the Michael product was assigned by TDDFT
simulation of the ECD spectrum. And the Michael products can be readily converted into
analogs of cycloalkano[b] fused pyrrolidines.
DOI: 10.1039/c3nj00000x
www.rsc.org/njc
Introduction
Therefore, much effort has been directed to determine new
transformations to prepare these powerful intermediates.5 To
date, poor enantioselectivity is achieved in most cases when
25 the cycloheptanone or cyclooctanone serves as the Michael
donor.6 Recently, Wang reported one example of secondary
Over the past decade, chemists have witnessed
a rapid
development in organocatalysis, a powerful and attractive field
involving the synthesis of chiral building blocks, natural products,
5 and biologically active compounds using inexpensive and
environmentally benign organocatalysts under mild conditions.
Numerous elegant enantiocontrol organocatalytic methodologies
have been developed.1 The Michael reaction has been widely
used to build valuable carbon-carbon bonds in modern organic
10 chemistry.2 Accordingly, the asymmetric organocatalytic Michael
reaction has attracted considerable attention, and significant
progress has been widely exploited over the past 10 years with a
diverse combination of Michael donors and acceptors.3
Specifically, the asymmetric organocatalytic Michael addition of
15 carbonyl compounds to nitroalkenes has stimulated extensive
interest because the chiral adducts (γ-nitrocarbonyl compounds)
serve as key precursors of various key complex organic targets.4
amine catalysed asymmetric Michael addition
of
cycloheptanone with nitroolefin, giving excellent
enantioselectivity.6e However, numerous biologically active
30 compounds, both naturally occurring and artificial, contain
complex seven- and eight-membered carbocycles in their
core structures, such as cycloalkano[b]fused pyrrolidines
(Figure 1)7 and α-methylene butyrolactones8. Consequently,
the development of an efficient organocatalytic method for
35 the Michael reaction of cycloheptanone and cyclooctanone
with electrophiles with high enantioselectivity remains
challenging and indispensable.
Results and Discussion
We initiated our study using catalyst
3 for the Michael
H
N
OH
O
N
40 reaction of cycloheptanone 1a with nitrodiene 2a (Scheme
O
1).9 Table 1 shows that the secondary amine catalysts L–
prolinol 3a, L–proline 3b, Jørgensen-Hayashi catalyst 3c
,
N
O
N
CO2H
H
and MacMillan catalyst 3d were almost completely inactive
(entries 1 to 4) for the Michael transformation. The
45 multifunctional Xu catalysts 3e and 3f led to moderate
catalytic activity (10% and 52% yield) and good
enantioselectivity (70% ee and 67% ee) (entries 5 and 6).
The chiral primary amine catalyst 3g and the chiral primary
amine-thiourea bifunctional catalyst 3h could not promote
50 the reaction (entries 7 and 8). By contrast, higher selectivity
were obtained using the Cinchona alkaloid-based primary
(-)-Actinophyllic Acid
Gelsemine
NH
n
analogues of cycloalkano[b]
fused pyrrolidines
O
O
H2N
H
O
N
H
OH
O
H
N
N
CO2Me
H
H
, 3j, 3k, , which promoted the
3l, and 3m 10
Daphnipaxinin
Prunifoline D
amine catalysts 3i
formation of 5a with high diastereoselectivity (9:1 dr to 29:1
Figure 1. Examples of biologically active compounds
20 containing seven- and eight-membered carbocycles
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New J. Chem., 2013, 37, 1‐3 | 1

Page 3 of 7
New Journal of Chemistry
loadings of catalysts 3i
the results showed that the yield increased with
increasingcatalyst loading. The yield and enantioselectivity
, 3k, and 3m were then verified, and
dr) and enantioselectivity (67% ee to 88% ee), although low
yields (11% to 19%) were obtained (entries 9 to 13). The
loadings of catalysts 3i 3k, and 3m were then verified, and
View Article Online
DOI: 10.1039/C4NJ01206B
,
10 rose from19% and 86% ee to 73% and 89% ee, respectively,
when the loading amount of catalyst 3m increased from 20
mol% to 50 mol% (entries 13 to 18). Additionally,
increasing the reaction temperature led to higher yield but
lower selectivity (entry 19 vs. entry 17). Notably, xylene and
15 PhCO2H were found to be the comparatively suitable solvent
and additive, respectively, among a series of organic
solvents and acids (see the Supporting Information).11 Thus,
an efficient catalyst 3m / PhCO2H / xylene system was
developed for the highly enantioselective Michael reaction.
the results showed that the yield increased with increasing
5
Table 1. Catalyst screening and reaction optimizationa
NO2
O
O
catalyst
PhCO2H
3
4a
NO2
xylene, 3d
1a
2a
5a
Entry
Catalyst
T (℃)
Yieldd (%)
dre
eee (%)
(anti)
n.d.
n.d.
n.d.
n.d.
70
(anti:syn)
n.d.
n.d.
n.d.
n.d.
4:1
1
2
3
4
5
6
7
8
9
10
11
12
13
14b
15b
16b
17c
18c
19c
3a
3b
3c
3d
3e
3f
3g
3h
3i
3j
3k
3l
3m
3i
3k
3m
3k
3m
3k
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25
50
5<
trace
trace
trace
10
20
O
Ph
Ph
OTMS
N
N
OH
OH
N
H
H
H
3a
3b
3c
52
3:1
67
O
N
N
N
trace
trace
16
12
11
12
19
23
25
37
48
73
70
n.d.
n.d.
24:1
9:1
29:1
9:1
13:1
8:1
8:1
n.d.
n.d.
85f
S
S
N
N
N
N
H
H
H
3d
3e
3f
69f
CF3
S
88
67
N
H
N
H
CF3
H2
N
NH2
NH2
86
3g
3h
83f
89
88
90
89
NH2
OMe
H
H
11:1
6:1
7:1
N
N
N
NH2
3k
N
H
NH2
N
N
3i
3j
4:1
83
aUnless otherwise stated, the reaction was conducted by stirring in
xylene (0.5 ml) using 1a (0.5 mmol) and 2a (0.13 mmol) with 20 mol%
catalyst 3 and 20 mol% PhCO2H 4a at room temperature. b30 mol%
catalyst 3 and 30 mol% PhCO2H 4a were used. c50 mol% catalyst 3 and 50
mol% PhCO2H 4a were used. dIsolated yield. eDetermined by HPLC
analysis on a Chiralcel AS‐H. fThe opposite configuration.
NH2
H
OMe
H
N
N
N
NH2
N
OMe
3l
3m
Scheme 1. The catalysts used in this study
Table 2. Substrate scope of nitrodienes in Michael reactiona
NO2
O
O
3m, 4a
NO2
R1
n
R1
xylene, RT, 3d
n
1
2
5
c
d
d
Entry
n/1
R1
Product
Yield (%)
dr (anti:syn)
ee (%) (anti)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
2/1b
2/1b
2/1b
2/1b
2/1b
2/1b
C6H5
5ab
5bb
5cb
5db
5eb
5fb
73
72
67
80
75
62
78
75
60
84
78
88
45
41
23
37
23
83
7:1
8:1
7:1
7:1
6:1
6:1
7:1
6:1
6:1
8:1
9:1
2:1
23:1
47:1
99:1
99:1
26:1
99:1
89
90
87
89
90
88
86
91
86
80
83
78
92
93
91
92
94
99
4‐MeC6H4
4‐MeOC6H4
4‐FC6H4
4‐ClC6H4
4‐BrC6H4
3‐FC6H4
3‐ClC6H4
3‐BrC6H4
Pr
iPr
CO2Et
C6H5
4‐MeC6H4
4‐FC6H4
4‐ClC6H4
4‐BrC6H4
iPr
5gb
5hb
5ib
5jb
5ka
5la
5ma
5na
5oa
5pa
5qa
5ra
aUnless otherwise stated, the reaction was conducted by stirring in xylene(0.5 ml) using 1 (0.5 mmol) and 2 (0.13 mmol) with 30 mol% catalyst 3m and
30 mol% PhCO2H 4a at room temperature. In the case of racemic samples, 50 mol% pyrrolidine and 50 mol% PhCO2H 4a were used. b50 mol% catalyst
3m and 50 mol% PhCO2H 4a were used. cIsolated yield. dDetermined by HPLC analysis.
This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2013
New J. Chem., 2013, 37, 1‐3 | 2

New Journal of Chemistry
Page 4 of 7
The scope of the reaction with respect to nitrodiene was 25 which resulted in the additional products 5s and 5t with high
explored using the established optimized reaction conditions
(Table 2). With cycloheptanone 1a aryl and alkyl
substituents were well tolerated on nitrodiene reactants and
provided the respective Michael product 5a with moderate
ee values of 98% and 94% and dr values of 83:1 and 10:1,
View Article Online
,
respectively. Acyclic ketone 1e also served as a suitable
DOI: 10.1039/C4NJ01206B
carbon nucleophile for the Michael reaction, and afforded
5
–
l
the corresponding adduct 5u with good results in terms of
to high yields (60% to 88%), diastereoselectivities (2:1 to 30 yield
(67%),
diastereoselectivity
(9:1
dr),
and
9:1 dr), and enantioselectivities (78% to 91% ee) (entries 1
to 12). Apparently, electron-donating and electron-
withdrawing substituents on the aromatic ring of the
enantioselectivity (96% ee).
NO2
O
O
10 nitrodienes had limited effect on yield and selectivity
(entries 1 to 9). Accordingly, the nitrodiene scope was
further explored using cyclooctanone 1b as substrate (entries
13 to 18). In this case, various nitrodiene derivatives with
different substitution patterns on the aromatic ring all
15 provided the expected products 5m to 5q with excellent
levels of diastereoselectivity (23:1 to 99:1 dr) and
enantioselectivity (91% to 94% ee) (entries 13 to 17).
Notably, alkyl-substituted nitrodiene could also be used as
reaction partner, and the product 5r was obtained in 83%
20 yield with 99:1 dr and 99% ee (entry 18). Compared with the
previous results with 1a, the use of 1b as substrate generally
led to enhanced diastereoselectivities and enantioselectivities.
The macrocyclic ketones 1c and 1d could also readily
participate in the Michael transformation as nucleophiles,
3m (30 mol%)
4a (30 mol%)
NO2
5s
, 20% yield
83:1 dr, 98% ee
xylene, RT, 3d
1c
2a
NO2
O
O
3m (30 mol%)
4a (30 mol%)
NO2
5t
,
26% yield
10:1 dr, 94% ee
xylene, RT, 3d
1d
2a
O
NO2
3m (50 mol%)
4a (50 mol%)
O
NO2
5u
, 67% yield
9:1 dr, 96% ee
xylene, RT, 3d
1e
2a
35 Scheme 2. Further investigation of the substrate scope
Table 3. Substrate scope of nitroolefins in Michael reactiona
R3
NO2
O
O
3m, 4a
R2
NO2
R2
n
xylene, RT, 3d
n
R3
1
6
7
c
d
d
Entry
n/1
R2
R3
Product
Yield (%)
dr (anti:syn)
ee (%) (anti)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
1/1a
2/1b
2/1b
2/1b
2/1b
2/1b
2/1b
2/1b
1/1a
2/1b
C6H5
4‐MeC6H4
4‐MeOC6H4
4‐FC6H4
4‐ClC6H4
4‐BrC6H4
3‐MeOC6H4
3‐BrC6H4
C6H5
4‐MeC6H4
4‐MeOC6H4
4‐FC6H4
4‐BrC6H4
3‐ClC6H4
3‐BrC6H4
C6H5
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
7ab
7bb
7cb
7db
7eb
7fb
70
69
84
76
79
79
75
50
67
60
57
39
54
58
50
34
38
19:1
30:1
20:1
38:1
24:1
38:1
22:1
57:1
86:1
59:1
>100:1
43:1
26:1
>100:1
16:1
3:1
89
84
90
92
87
83
81
86
99
95
99
99
99
>99
98
93
99
7gb
7hb
7ia
7ja
7ka
7la
7ma
7na
7oa
7pa
7qa
Me
Me
C6H5
8:1
aUnless otherwise stated, the reaction was conducted by stirring in xylene(0.5 ml) using 1 (0.5 mmol) and 6 (0.13 mmol) with 30 mol% catalyst 3m and 30
mol% PhCO2H 4a at room temperature. In the case of racemic samples, 50 mol% pyrrolidine and 50 mol% PhCO2H 4a were used. b50 mol% catalyst 3m and
50 mol% PhCO2H 4a were used. cIsolated yield. dDetermined by HPLC analysis.
Scheme 3. Proposed transition state for the reaction
OMe
H
NO2
N
O
O
N
O
H
NO2
NH
O
N
3m / 4a
1a
2a
5a
ttack
Si- face a
TS
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New J. Chem., 2013, 37, 1‐3 | 3

Page 5 of 7
New Journal of Chemistry
NO2
O
O
NO2
3m, 4a
View Article Online
DOI: 10.1039/C4NJ01206B
xylene, RT, 3d
1
2a
5a
10 mmol scale
1.75g
2.09g (73%)
7:1 dr
89% ee
NO2
Bn
N
O
N
H
H
Zn, 4N HCl
EtOH, 40h, 35℃
1) NaBH4, EtOH, 45 min, 0℃
H
2) BnBr, KOH, EtOH, 24h, rt
5a
89% ee, 7:1 dr
8a, 95% yield,
85% ee, 99:1 dr
9a, 46% yield,
83% ee, 4:1 dr
Scheme 4. Enantioselective gram-scale synthesis of 5a, and derivatization of Michael adduct 5a to cycloalkano[b]fused
pyrrolidine 9a11
With the above success, the reaction scope was further
The enantioselective Michael reaction can be performed
extended to nitroolefins. As illustrated in Table 3, the reaction successfully on gram-scale to obtain 2.09 g of 5a (73% yield)
of cycloheptanone 1a or cyclooctanone 1b with nitroolefins with the same diastereoselectivity and enantioselectivity under
were performed under the above optimal reaction conditions. modified conditions (Scheme 4). The synthetic utility of this
The reactions proceeded smoothly in moderate to high yields Michael reaction was also demonstrated in the synthesis of
(up to 84% yield), high to excellent diastereoselectivities (up to chiral cycloalkano[b]fused pyrrolidine 9a (Scheme 4).13 The
>100: 1 dr) and good to excellent enantioselectivities (up to >99 transformation involves the Zn/HCl-mediated reductive
ee) (entries 1 to 15). It is noteworthy that reactions between 1b cyclization of adduct 5a to obtain imine 8a in 95% yield. A
and nitroolefins gave better results to those nitrodienes were reduction of imine 8a with NaBH4 followed by Bn protection
used as the nucleophiles(table 3, entries 9 to 15 vs table 2, resulted in 9a with good overall yield and without racemization.
entries 13 to 18), and reactions between 1a and nitroolefins
obtained better diastereoselectivities than those between 1a and
nitrodienes (table 3, entries 1 to 8 vs table 2, entries 1 to 9).
Conclusions
In summary, an organocatalytic enantioselective Michael
reaction of nucleophiles, cycloheptanone or cyclooctanone,
with nitrodienes and nitroolefins catalyzed by hydroquinine-
based primary amine catalyst has been established. The
corresponding adducts were obtained in good yields (up to 88%)
with good to excellent diastereoselectivities (up to >100:1 dr)
and good to excellent enantioselectivities (up to >99% ee). The
product can be readily converted into analogs of cycloalkano[b]
fused pyrrolidines, which further enhances the utility of this
transformation for the synthesis of potentially valuable chiral
molecules.
The reactions of β-disubstituted nitroalkenes including β-
methyl nitroalkene (table 3, entries 16 and 17) reacted
successfully to give the corresponding products 7p and 7q in
good to high diastereoselectivities with high to excellent
enantioselectivities.
The absolute configuration (AC) of the Michael product 5a
was determined to be S, S by comparing the experimental CD
spectrum with the results of time-dependent density functional
theory (TDDFT) calculations of electronic circular dichroism
(ECD) spectra.11, 12 As shown in Figure 2 (Figure 6S), in the
selected data in the 200-390 nm UV region, the experimental
CD spectrum is consistent with the calculated data of 1-SS.
Then, a transition state model was proposed (Scheme 3).
Nitrodiene 2a was activated well through the hydrogen-bonding
interaction between the protonated bridgehead nitrogen atom of
3m and nitro group of 2a. Therefore, the enamine formed from
Experimental section
General information
The 1H NMR and 13C NMR spectra were recorded in
deuterated solvents and are reported in ppm relative to
tetramethylsilane. GC-MS experiments were performed on a
GC system with a mass selective detector. HRMS data were
3m and 1a attacked the activated 2a from the Si face to afford
the major stereoisomer of Michael adduct 5a with the
configuration of (S, S).
measured using
a
TOF mass spectrometer. Column
chromatography and flash chromatography experiments were
performed on silica gel (200-300 mesh) eluting with ethyl ether
and petroleum ether. TLC experiments were carried out on
glass-backed silica plates. In each case, enantiomeric ratio was
determined on a chiral column in comparison with authentic
racemates by chiral HPLC. Chemicals were used without
purification as commercially available. Nitrodienes,14 and
organocatalysts 3d 15
,
3e- , , 3i- ,
3f 16 3h 17 3l 18 3m19 were
synthesized according to literature.
Typical experimental procedure for the Michael reaction
Xylene (0.5mL) was added to a mixture of cycloheptanone 1a
Figure 2. Experimental (dotted trace) and calculated ECD spectra
(full trace) of the Michael product 5a
or cyclooctanone 1b (0.5 mmol) with nitrodienes
2 or
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New J. Chem., 2013, 37, 1‐3 | 4

New Journal of Chemistry
Page 6 of 7
nitroolefins
6 (0.126 mmol) in the presence of 30 mol % or 50
View Article Online
Badia and L. Carrillo, Synthesis 2007, 2065; (e) B. Westermann, M.
DOI: 10.1039/C4NJ01206B
mol % catalyst 3m and 30 mol % or 50 mol % PhCO2H 4a at
room temperature with vigorous stirring. The reaction
conversion was monitored by GC-MS. After three days, the
reaction mixture was extracted with DCM, washed with water,
dried and concentrated. The residue was purified by flash
chromatography on silica gel (ether/petroleum ether = 1:4 to
1:2 as eluent) to give the slightly white solid of the Michael
Ayaz and S. S. van Berkel, Angew. Chem. Int. Ed. 2010, 49, 846; (f) J.
Wang, P. Li, P. Y. Choy, A. S. C. Chan and F. Y. Kwong,
ChemCatChem 2012, 4, 917; (g) C. F. Nising and S. Bräse, Chem.
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4
For selected reviews, see: (a) O. M. Berner, L. Tedeschi and D.
Enders, Eur. J. Org. Chem. 2002, 1877; (b) S. Sulzer-Mosse and A.
Alexakis, Chem. Commun. 2007, 3123; (c) D. Roca-Lopez, D.
Sadaba, I. Delso, R. P. Herrera, T. Tejero and P. Merino, Tetrahedron:
addition products 5a
7k 7n 7q, the slightly yellow liquid products 5j
7g and colorless oil 7c 7l. The enantiomeric excesses (% ee)
–
5i
,
5m
–
5q
,
7a
–
7b
,
7e
–
7f
,
7i
–
,
–
–
5l
,
5r
,
,
Asymmetry 2010
For selected reviews, see: (a) C. Grondal, M. Jeanty and D. Enders,
Nat. Chem. 2010 , 167; (b) Y. Zhang and W. Wang, Catal. Sci.
Technol. 2012 , 42.
, 21, 2561.
was determined by HPLC analysis using chiral stationary
phases.
5
6
,
2
,
2
Acknowledgements
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Chem. 2004, 1577; (b) J. Wang, H. Li, B. Lou, L. Zu, H. Guo and W.
This work was supported by the NSFC (21202149), the
Zhejiang
Natural Science Foundation (Y4110348), the
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and G. Zhao, J Mol Catal A -Chem. 2007
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12, 4321; (c) L. Gu, Y. Wu, Y. Zhang
Foundation of Zhejiang Education Committee (Y201225109),
the Foundation of Zhejiang Key Course of Chemical
Engineering and Technology, and the Foundation of Zhejiang
Key Laboratory of Green Pesticides and Cleaner Production
Technology.
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,
6
,
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