Asymmetric Ring-Opening of Cyclopropyl Ketones with Thiol, Alcohol, and Carboxylic Acid Nucleophiles Catalyzed by a Chiral N,N′-Dioxide-Scandium(III) Complex

Article abstract of DOI:10.1002/anie.201506909

A highly efficient asymmetric ring-opening reaction of cyclopropyl ketones with a broad range of thiols, alcohols and carboxylic acids has been first realized by using a chiral N,N′-dioxide-scandium(III) complex as catalyst. The corresponding sulfides, ethers, and esters were obtained in up to 99 % yield and 95 % ee. This is also the first example of one catalytic system working for the ring-opening reaction of donor-acceptor cyclopropanes with three different nucleophiles, let alone in an asymmetric version.

Full text of DOI:10.1002/anie.201506909

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Angewandte
Communications
International Edition: DOI: 10.1002/anie.201506909
German Edition: DOI: 10.1002/ange.201506909
Asymmetric Ring Opening
Asymmetric Ring-Opening of Cyclopropyl Ketones with Thiol,
Alcohol, and Carboxylic Acid Nucleophiles Catalyzed by a Chiral N,N’-
Dioxide–Scandium(III) Complex
Yong Xia, Lili Lin, Fenzhen Chang, Xuan Fu, Xiaohua Liu,* and Xiaoming Feng*
Abstract: A highly efficient asymmetric ring-opening reaction
of cyclopropyl ketones with a broad range of thiols, alcohols
and carboxylic acids has been first realized by using a chiral
N,N’-dioxide–scandium(III) complex as catalyst. The corre-
sponding sulfides, ethers, and esters were obtained in up to
reported to date. This could be assigned to the following
reasons: i) For thiols, the strong coordination ability of sulfur
atom to the central metal might poison the catalyst when
a Lewis acid is used as catalyst; ii) For carboxylic acids, the
reaction usually requires severe conditions because of their
weak nucleophilic nature, which makes it difficult to balance
the reactivity and stereocontrol. Furthermore, searching for
a catalyst system that could work well on not only sulfur-
containing nucleophiles but also oxygen-containing nucleo-
philes is challenging. As part of a program devoted to
expanding new synthetic methods involving D-A cyclopro-
panes, we recently described an enantioselective ring-open-
ing/cyclization of cyclopropyl ketones with primary amines
using a chiral N,N’-dioxide–scandium(III) complex, and the
corresponding 2,3-dihydropyrroles were obtained in excellent
9
9% yield and 95% ee. This is also the first example of one
catalytic system working for the ring-opening reaction of
donor–acceptor cyclopropanes with three different nucleo-
philes, let alone in an asymmetric version.
C
yclopropanes have proven to be powerful synthetic build-
[
1]
ing blocks. In particular, the ring-opening reactions of
[2–7]
donor–acceptor (D-A) cyclopropanes
provide access to
a myriad of functionalized carbon skeletons and have
attracted extensive attention. Ring-opening reactions initi-
ated by sulfur- and oxygen-containing nucleophiles have been
found to be a very useful transformation in the synthesis of g-
[10]
outcomes (Scheme 1b). In continuation of our studies on
ring-opening of cyclopropyl ketones, herein we report our
efforts on developing the catalytic asymmetric direct ring-
opening reaction of cyclopropyl ketones with thiol, alcohol,
and carboxylic acid nucleophiles catalyzed by a chiral N,N’-
[
8,9]
thio and g-oxy functionalized carbonyls.
For example, the
(
S)-proline and Ca(acac) -catalyzed racemic reaction with
2
[7k]
[7l]
thiol nucleophiles were reported by Wang
and Nolin,
[11]
respectively. Moreover, the opening of 1-nitro-cyclopropane-
carboxylates with phenols for synthesizing the norepinephr-
ine reuptake inhibitor atomoxetine was developed by Char-
dioxide–scandium(III) complex (Scheme 1c).
Initially, cyclopropyl ketone 1a and thiophenol 2e were
chosen as model substrates to optimize the reaction con-
ditions. At first, various metal salts complexing with N,N’-
dioxide l-PiPr3 derived from (S)-pipecolic acid (Pi) were
evaluated in the presence of LiCl in CHCl CHCl at 608C
[
7n]
ette.
An intramolecular nucleophilic ring-opening deal-
kyoxycarbonylation of cyclopropane hemimalonate to the
synthesis of g-substituted butanolides under microwave
2
2
[7q]
irradiation was also documented by Kerr (Scheme 1a).
(Table 1, entries 1–3). After 48 h, the complexes of Yb(OTf)3
Although the reactions of D-A cyclopropanes with sulfur-
and oxygen-containing nucleophiles have been developed, no
examples of catalytic asymmetric ring-opening of D-A cyclo-
propanes with thiols, alcohols, or carboxylic acids have been
and Ni(ClO ) ·6H O gave moderate yields and poor ee values
4
2
2
(entries 1,2). To our delight, the l-PiPr -Sc(OTf) complex
3
3
was more effective at promoting the reaction, and the desired
product 3ae was obtained in 92% yield with 91% ee. The
structure of the ligands were then investigated. It was found
that the steric hindrance of the amide moieties, as well as the
amino acid backbone of the ligands, influenced the reaction
greatly. Decreasing the steric hindrance of amide substituent,
[
*] Y. Xia, Dr. L. L. Lin, F. Z. Chang, X. Fu, Prof. Dr. X. H. Liu,
Prof. Dr. X. M. Feng
Key Laboratory of Green Chemistry & Technology,
Ministry of Education, College of Chemistry,
Sichuan University
Chengdu 610064 (China)
E-mail: liuxh@scu.edu.cn
or using (S)-proline derived l-PrPr and l-ramipril derived l-
3
RaPr3 as ligands resulted in lower reactivity and poorer
enantioselectivity (entries 4–6). When performed at 358C, the
reaction could also occur and 3ae was isolated in 80% yield
with 92% ee after prolonging the reaction time to 96 h
(entry 7). Other reaction conditions, such as solvent and
additive, were also investigated, but no better results were
obtained (see the Supporting Information for details). There-
fore, the optimized conditions entailed the use of l-PiPr3-
Sc(OTf) as catalyst and LiCl as additive in CHCl CHCl at
xmfeng@scu.edu.cn
Prof. Dr. X. M. Feng
Collaborative Innovation Center of
Chemical Science and Engineering
Tianjin (China)
and
3
2
2
State Key Laboratory of Applied Organic Chemistry,
Lanzhou University
6
08C for 48 h (entry 3).
Lanzhou 730000 (China)
With the optimized conditions established, the substrate
scope of thiol nucleophiles was explored. As shown in Table 2,
a wide range of thiols including aromatic and aliphatic
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201506909.
1
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Angew. Chem. Int. Ed. 2015, 54, 13748 –13752

Angewandte
Chemie
stereoselectivities, nei-
ther the steric hin-
drance nor the elec-
tronic nature of the sub-
stituents at the aromatic
ring of thiolphenols had
any obvious influence
on enantioselectivities
(
entries 1–9).
More-
heteroaromatic
naphthyl-substi-
over,
and
tuted thiols were also
suitable substrates,
giving the desired acy-
clic products 3aj–3al in
7
9
4–98% yields with 90–
1% ee (entries 10–12).
The aliphatic thiols,
including primary, acy-
clic, and cyclic secon-
dary thiols exhibited
high levels of asymmet-
ric induction, affording
the corresponding sul-
fides 3am–3ar in 90–
9
5% ee (entries 13–18).
Scheme 1. Ring-opening reactions of D-A cyclopropanes with nucleophiles.
It is particularly note-
worthy that tertiary sub-
stituted tert-butyl mer-
captan was also compatible, and the product 3as was obtained
in 86% ee, albeit with a moderate yield (55%, entry 19).
Furthermore, when the reaction of 1a with 2e was carried out
on a gram scale, the corresponding product 3ae was
accomplished in 83% yield with 94% ee (entry 20).
Subsequently, the substrate scope of cyclopropyl ketones
was examined, and the results are listed in Table 3. Cyclo-
propyl ketones with either electron-rich or electron-poor
[
a]
Table 1: Optimization of the reaction conditions.
1
substituted aryl R at the 2-position could be efficiently
converted to the corresponding products in good yields (62–
9
4%) with excellent ee (90–95%, entries 1–9). When naph-
thyl-substituted substrate was injected to the reaction, the
opening product 3ke was obtained in 92% yield with 88% ee
[
b]
[c]
Entry
Metal
L
Yield [%]
ee [%]
(entry 10). The electronic nature of the substituent at the para
1
2
3
4
5
6
Ni(ClO ) ·6H O
l-PiPr3
42
51
92
75
68
56
80
8
4
2
2
position of the benzoyl group had no obvious effect on the
reactivities and enantioselectivities of this reaction
Yb(OTf)3
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
l-PiPr3
36
91
79
88
77
92
l-PiPr3
l-PiPr2
l-RaPr3
l-PrPr3
l-PiPr3
(entries 11,12). The 2-phenyl-cyclopropane-1,1-dimethylke-
tones, 2-methyl-cyclopropane-1,1-diphenylketones, and 2-
phenyl-cyclopropane-1,1-dicarboxylic acid diesters were also
[
d]
[12]
7
investigated, but no ring-opening products were observed.
Encouraged by the results obtained from thiols, we
extended this catalytic system to the ring-opening reactions
of cyclopropyl ketones with oxygen-containing nucleophiles.
Aliphatic alcohols proceeded smoothly to give the corre-
sponding products in good yields (65–94%) with excellent
enantiomeric excesses (90–92%; Table 4, entries 1–8).
Extending the carbon chains of alcohols had no obvious
influence on the enantioselectivities (entries 1–4). Besides the
acyclic substituted alcohols, cyclic substituted alcohols also
performed well in this catalytic system, giving the opening
[
(
(
a] Unless otherwise noted, all reactions were carried out with 1a
0.25 mmol), 2a (0.1 mmol), l-metal (1.1:1, 10 mol%), and LiCl
0.1 mmol) in CHCl CHCl (0.5 mL) under nitrogen at 608C for 48 h.
2
2
[
b] Yield of isolated product. [c] Determined by chiral HPLC analysis on
a chiral stationary phase. [d] At 358C for 96 h. OTf=trifluoromethane-
sulfonate.
substituents were suitable substrates for the reaction. Gen-
erally, thiophenols showed higher reactivities and gave better
yields than aliphatic substituted ones. In respect to the
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www.angewandte.org 13749

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Angewandte
Communications
[
a]
[a]
Table 2: Substrate scope for thiols.
Table 4: Substrate scope for alcohols and carboxylic acids.
3
[b]
[c]
3
[b]
[c]
Entry
R
3
Yield [%]
ee [%]
Entry
R
X
3 or 4
Yield [%]
ee [%]
1
2
3
4
Ph
4-MeC H
4-MeOC H
4-FC H
4-ClC H
4-BrC H
3-ClC H
2-ClC H
3aa
3ab
3ac
3ad
3ae
3af
3ag
3ah
3ai
94
97
95
84
92
90
90
83
95
98
95
74
78
94
69
79
89
90
55
83
92
91
89
91
91 (R)
92
93
92
92
90
91
90
95
95
95
90
93
91
1
2
3
4
5
6
7
Me
Et
n-Pr
n-octanyl
Bn
cyclobutyl
cyclopentyl
cyclohexyl
Ph
Me
Et
O
O
O
O
O
O
O
O
4aa
4ab
4ac
4ad
4ae
4af
4ag
4ah
4ai
4aj
4ak
4al
4am
4an
4ao
69
78
65
78
60
72
94
78
62
90
90
98
99
96
99
91
92
92
91
90
92
92
91
50
76
77
82
83
69
72
6
4
6
4
6
4
[
d]
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
6
4
6
4
6
4
[
d]
e]
[
6
4
8
9
[
2-MeC H
O
6
4
f]
f]
f]
0
1
2
3
4
5
6
7
8
9
0
1-naphthyl
2-naphthyl
2-thienyl
Et
3aj
3ak
3al
10
11
12
13
14
15
COO
COO
COO
COO
COO
COO
[
[
n-heptyl
Bn
Ph
[
e]
[f]
f]
[f,g]
3am
3an
3ao
3ap
3aq
3ar
3as
3ae
[
Bn
[
[
[
[
[
[
e]
f]
EtO CCH CH
2
iPr
cyclopentyl
cyclohexyl
tBu
cyclohexyl
2
2
e]
e]
f]
[a] Reaction conditions were similar to that in Table 2 except the reaction
time was 96 h. [b] Yield of isolated product. [c] Determined by chiral
HPLC analysis on a chiral stationary phase. [d] Reaction time was 168 h.
[e] Reaction time was 48 h. [f] 1a (0.4 mmol), l-PiPr
5
86
94
g]
-Sc(OTf) (1:1,
3 3
4-ClC H
6
4
mol%), 24 h. [g] l-PiPr -Sc(OTf) (1:1, 10 mol%), 48 h.
3
[
a] Unless otherwise noted, all reactions were carried out with 1a
(
(
0.25 mmol), 2a (0.1 mmol), l-PiPr -Sc(OTf) (1.1:1, 10 mol%), and LiCl
3 3
0.1 mmol) in CHCl CHCl (0.5 mL) under nitrogen at 608C for 48 h.
2
2
[
b] Yield of isolated product. [c] Determined by chiral HPLC analysis on
participate in this reaction and they generated the opening
products in excellent yields with moderate to good enantio-
selectivities (Table 4, entries 10–15). Extending the alkyl
length of carboxylic acids slightly improved the results
a chiral stationary phase. [d] The absolute configuration of 3ae was
determined to be R by X-ray crystallographic analysis of the corre-
sponding sulfone 6. [e] Reaction time was 72 h. [f] Reaction time was
9
6 h. [g] The reaction was carried out on a gram scale.
(entries 10–12). An 83% enantiomeric excess was obtained
when phenylacetic acid was employed (entry 13). A moderate
ee (69%) and excellent yield (96%) were observed when
aromatic substituted benzoic acid was applied (entry 14).
Notably, the reaction could be extended to cyclic substituted
acids, such as cyclohexane carboxylic acid, and the corre-
sponding product 4ao was isolated in nearly quantitative yield
with 72% ee (entry 15).
[
a]
Table 3: Substrate scope for cyclopropyl ketones.
1
2
[b]
[c]
Entry
R
R
3
Yield [%]
ee [%]
To evaluate the synthetic potential of this method, several
transformations were carried out. The sulfide product 3ae
could be efficiently transformed into sulfoxide 5 by using
aqueous H O (30%) as an oxidant in the presence of copper–
1
2
3
4
4-MeC H
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3be
3ce
3de
3ee
3 fe
3ge
3he
3ie
83
94
90
93
88
80
76
62
68
92
87
85
91
93
94
91
93
90
92
95
92
88
95
95
6
4
3-MeC H
6
4
3-MeOC H
6
4
2
2
[13]
2-MeC H
6
4
Schiff base. Meanwhile, 3ae could also be transformed to
sulfone 6 using m-CPBA as an oxidant through an oxidation
process. The absolute configuration of 6 was unambiguously
[
[
[
[
[
d]
d]
d]
d]
e]
5
6
7
8
9
1
1
1
4-FC H
6
4
4-ClC H
6
4
4-BrC H
6
4
[14]
confirmed as R by X-ray diffraction analysis.
In the
3-ClC H
6
4
3,4-Cl C H
3
3je
3ke
3le
presence of aqueous NaOH, one benzoyl group of 3ae
could be removed, giving g-sulfide mono-carbonyl compound
7. Baeyer–Villiger oxidation of 7 proceeded with m-CPBA to
afford g-sulfonyl ester 8 in 69% yield with 94% ee.
Furthermore, amide 9 could be easily achieved from 7
through an oximation/Beckmann rearrangement sequence
2
6
0
1
2
2-naphthyl
Ph
Ph
4-MeC H
4-FC H
6
4
3me
6
4
[
a] Reaction conditions were the same as that in Table 2. [b] Yield of
isolated product. [c] Determined by chiral HPLC analysis on a chiral
stationary phase. [d] Reaction time was 96 h. [e] Reaction time was
(Scheme 2a). The ester 4am also could be efficiently con-
1
68 h.
verted to chiral g-hydroxyl ketone 10 in 88% yield with
maintained enantioselectivity by treatment with aqueous
NaOH (Scheme 2b).
In summary, we have realized the first catalytic asym-
metric ring-opening reaction of cyclopropyl ketones with
products 4af–4ah in 72–94% yields with 91–92% ee
entries 6–8). A yield of 62% with 50% ee was observed
when phenol was tested (entry 9). Carboxylic acids could also
(
1
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[
[
2] For the representative reviews, see: a) H. U. Reissig, R. Zimmer,
Chem. Rev. 2003, 103, 1151; b) T. P. Lebold, M. A. Kerr, Pure
Appl. Chem. 2010, 82, 1797; c) M. A. Cavitt, L. H. Phun, S.
France, Chem. Soc. Rev. 2014, 43, 804; d) T. F. Schneider, J.
Kaschel, D. B. Werz, Angew. Chem. Int. Ed. 2014, 53, 5504;
Angew. Chem. 2014, 126, 5608; e) H. K. Grover, M. R. Emmett,
M. A. Kerr, Org. Biomol. Chem. 2015, 13, 655.
3] For selected examples of [3+2] annulations with enol silyl ethers,
see: a) F. de Nanteuil, J. Waser, Angew. Chem. Int. Ed. 2011, 50,
1
2075; Angew. Chem. 2011, 123, 12281; b) H. Xu, J. Qu, S. Liao,
H. Xiong, Y. Tang, Angew. Chem. Int. Ed. 2013, 52, 4004; Angew.
Chem. 2013, 125, 4096; c) F. de Nanteuil, E. Serrano, D. Perrotta,
J. Waser, J. Am. Chem. Soc. 2014, 136, 6239; with aldehydes, see:
d) P. D. Pohlhaus, J. S. Johnson, J. Am. Chem. Soc. 2005, 127,
1
6014; e) P. D. Pohlhaus, S. D. Sanders, A. T. Parsons, W. Li, J. S.
Johnson, J. Am. Chem. Soc. 2008, 130, 8642; f) A. T. Parsons, J. S.
Johnson, J. Am. Chem. Soc. 2009, 131, 3122; g) S. Xing, W. Pan,
C. Liu, J. Ren, Z. Wang, Angew. Chem. Int. Ed. 2010, 49, 3215;
Angew. Chem. 2010, 122, 3283; with aldimines, see: h) S. K.
Jackson, A. Karadeolian, A. B. Driega, M. A. Kerr, J. Am.
Chem. Soc. 2008, 130, 4196; i) A. T. Parsons, A. G. Smith, A. J.
Neel, J. S. Johnson, J. Am. Chem. Soc. 2010, 132, 9688; with
indoles, see: j) J. Zhu, Y. Liang, L. Wang, Z. Zheng, K. N. Houk,
Y. Tang, J. Am. Chem. Soc. 2014, 136, 6900, with nitrosoarenes,
see: k) S. Chakrabarty, I. Chatterjee, B. Wibbeling, C. G.
Daniliuc, A. Studer, Angew. Chem. Int. Ed. 2014, 53, 5964;
Angew. Chem. 2014, 126, 6074.
Scheme 2. a) Elaboration of a ring-opening product; b) transformation
of ester to g-hydroxyl ketone.
thiols, alcohols, and carboxylic acids by using a chiral N,N’-
dioxide–scandium(III) complex, offering a novel access to
a variety of chiral sulfides, ethers, and esters in moderate to
excellent yields (up to 99%) and excellent enantioselectivities
(
up to 95% ee). The process proceeded under mild conditions
[
4] For selected examples of [3 ++ 3] annulations with aromatic
azomethine imines, see: a) Y. Zhou, J. Li, L. Ling, S. Liao, X.
Sun, Y. Li, L. Wang, Y. Tang, Angew. Chem. Int. Ed. 2013, 52,
and the ring-opening products could be efficiently converted
to a series of g-substituted carbonyl compounds. This is also
the first example of one catalytic system working for the
catalytic asymmetric ring-opening reaction of D-A cyclo-
propanes with three different nucleophiles. Further studies on
related reactions are underway.
1
452; Angew. Chem. 2013, 125, 1492; with nitrones, see: b) I. S.
Young, M. A. Kerr, Angew. Chem. Int. Ed. 2003, 42, 3023;
Angew. Chem. 2003, 115, 3131; c) M. P. Sibi, Z. Ma, C. P.
Jasperse, J. Am. Chem. Soc. 2005, 127, 5764; d) Y. Kang, X. Sun,
Y. Tang, Angew. Chem. Int. Ed. 2007, 46, 3918; Angew. Chem.
2
007, 119, 3992; e) D. A. Dias, M. A. Kerr, Org. Lett. 2009, 11,
3
694; f) W. J. Humenny, P. Kyriacou, K. Sapeta, A. Karadeolian,
Experimental Section
M. A. Kerr, Angew. Chem. Int. Ed. 2012, 51, 11088; Angew.
Chem. 2012, 124, 11250; with azides, see: g) H. Zhang, Y. Luo, H.
Wang, W. Chen, P. Xu, Org. Lett. 2014, 16, 4896.
Conditions: Sc(OTf) (0.01 mmol), N,N’-dioxide ligand l-PiPr3
3
(
(
0.011 mmol), LiCl (0.1 mmol) and cyclopropyl ketone 1a
0.25 mmol) were stirred in CH Cl (0.5 mL) at 358C for 0.5 h
2
2
[
5] For selected examples of [3+4] annulations, see: a) O. A.
Ivanova, E. M. Budynina, Y. K. Grishin, I. V. Trushkov, P. V.
Verteletskii, Angew. Chem. Int. Ed. 2008, 47, 1107; Angew.
Chem. 2008, 120, 1123; b) A. O. Chagarovskiy, E. M. Budynina,
O. A. Ivanova, Y. K. Grishin, I. V. Trushkov, P. V. Verteletskii,
Tetrahedron 2009, 65, 5385; c) H. Xu, J. Hu, L. Wang, S. Liao, Y.
Tang, J. Am. Chem. Soc. 2015, 137, 8006.
under nitrogen atmosphere. After removing CH Cl2 in vacuum,
2
CHCl CHCl (0.5 mL) and substrate 2e (0.1 mmol) were added. The
2
2
reaction was stirred at 608C for 48 h, and then directly purified by
flash chromatography on silica gel (petroleum ether/ethyl ether=
1
5:1) to afford the desired product 3ae (92% yield, 91% ee).
[
[
6] For an example of [3+8] annulations: R. Tejero, A. Ponce, J.
Adrio, J. C. Carretero, Chem. Commun. 2013, 49, 10406.
Acknowledgements
7] For selected examples of ring-opening reactions with indoles,
see: a) M. R. Emmett, M. A. Kerr, Org. Lett. 2011, 13, 4180; b) F.
de Nanteuil, J. Loup, J. Waser, Org. Lett. 2013, 15, 3738; in
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Johnson, Org. Lett. 2013, 15, 2558; d) H. Xiong, H. Xu, S. Liao,
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We appreciate the National Natural Science Foundation of
China (Nos. 21172151, 21290182, and 21321061) for financial
support.
Keywords: asymmetric catalysis · cyclopropyl ketones ·
nucleophiles · ring opening · scandium catalysts
How to cite: Angew. Chem. Int. Ed. 2015, 54, 13748–13752
Angew. Chem. 2015, 127, 13952–13956
3
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Received: July 26, 2015
Revised: August 20, 2015
Published online: September 23, 2015
1
3752 www.angewandte.org
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2015, 54, 13748 –13752