Copper-Catalyzed Enantioselective Hetero-Diels-Alder Reaction of Danishefsky's Diene with Glyoxals

Article abstract of DOI:10.1021/acs.joc.5b02780

(Chemical Equation Presented) The highly enantioselective hetero-Diels-Alder reaction of Danishefsky's diene with glyoxals was developed by virtue of a readily accessible chiral copper catalyst. This efficient transformation provided a facile and scalable

Full text of DOI:10.1021/acs.joc.5b02780

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Note
Copper-Catalyzed Enantioselective Hetero-Diels-
Alder Reaction of Danishefsky's Diene with Glyoxals
Yanan Li, Yanbin Hu, Sheng Zhang, Jianan Sun, Lijun Li, Zhenggen Zha, and Zhiyong Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b02780 • Publication Date (Web): 10 Mar 2016
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Copper-Catalyzed Enantioselective Hetero-Diels-Alder
Reaction of Danishefsky's Diene with Glyoxals
Yanan Li, Yanbin Hu, Sheng Zhang, Jianan Sun, Lijun Li, Zhenggen Zha, Zhiyong Wang*
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Hefei National Laboratory for Physical Sciences at Microscale, CAS Key Laboratory of Soft
Matter Chemistry and Department of Chemistry & Collaborative Innovation Center of Suzhou
Nano Science and Technology, University of Science and Technology of China, Hefei, Anhui
230026, P. R. China
E-mail: zwang3@ustc.edu.cn
ABSTRACT: The highly enantioselective hetero-Diels-Alder reaction of Danishefsky’s diene with
glyoxals was developed by virtue of a readily accessible chiral copper catalyst. This efficient
transformation provided a facile and scalable access to a wide range of biologically active
dihydropyrones with high level of enantioselectivities. Moreover, the substrate scope of this reaction
could be extended to isatins with this catalytic system. More importantly, the mechanism involved in
this reaction was proposed on the basis of the unambiguous structures of intermediates.
The asymmetric hetero-Diels-Alder (HDA) reaction of Danishefsky’s diene with aldehydes or
1
α-ketoesters is a very important method to synthesize optically active dihydropyrones, which are
2
one of the most privileged substructures in natural products and medicinal compounds. In this
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4
area, various catalytic systems, including Lewis acid catalysts, Brønsted acid catalysts, have
been extensively exploited to obtain a diversity of chiral dihydropyrones. The Jørgensen group
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reported the first highly enantioselective HDA reaction of Danishefsky’s diene with ketones
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catalyzed by chiral copper (II) complex. After that, the HDA reaction of α-carbonyl esters was
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further developed by Loh. Recently, a chiral 3,3-dibromo-BINOL-Zn complex was found to be
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an efficient catalyst in various HDA reactions by Ding et al. Moreover, an impressive work in the
HDA reaction of substituted Danishefsky’s diene with aldehydes had been achevied in Feng group
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by using a chiral N,N-Dioxide/In(OTf) catalyst. However, to the best of our knowledge, the
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HDA reaction of Danishefsky’s diene with glyoxals has received far less attention. In the previous
work of Mikami, a chiral bis-trifluoromethanesulfonylamide was first employed to catalyze this
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HDA reaction of glyoxals (Scheme 1a). Nevertheless, there remains a great challenge to develop
a general method with broader substrate scope. In this context, we envisioned that our previously
used catalyst, which showed high performance in the HDA reaction of β,γ-unsaturated
3
h
α-ketoesters, might be applied in this reaction. Indeed, various of dihydropyrones were provided
with excellent enantioselectivities (up to 96% ee) and high yields (up to 96%) in the presence of
this efficient catalyst.
Scheme 1. Previous study and this work on Hetero-Diels-Alder reaction of Danishefsky’s
diene with glyoxals.
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First of all, we chose the 2-oxo-2-phenylacetaldehyde hydrate 1a and Danishefsky’s diene 2a as
3
h,10
the model substrate. Inspired by the previous work in our laboratory,
the chiral L1-Cu
complex was utilized to optimize this reaction (Table 1). Firstly, different solvents were screened
for this reaction. The results showed that ethers favored this reaction (entries 1-5). Then, different
ethers were further optimized and CPME proved to be the optimal solvent in terms of yield and
enantioselectivity (entry 8). Afterwards, different reaction temperature was examined (entries
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-12). When the reaction was performed under -25°C, a moderate yield and excellent
enantioselectivity were obtained. Lowering the temperature to -35°C resulted in a significantly
decrease in the reaction yield, albeit a slightly improved enantiomeric excess was observed
(
entries 11-12). The substitutions of aromatic ring in the chiral ligand were next explored. It was
found that the ligand bearing an electron-enriched aryl ring could give a better performance
compared with the electron-deficient one (entries 13-15). However, a satisfied result still could not
be obtained. Considering the detrimental effect of the crystal water on the stereoselectivity of this
reaction, different water scavengers were screened (entries 16-18). To our delight, not only the
enantioselectivity was significantly improved to 95% ee but also the yield was remarkably
increased to 86% when 4Å molecular sieve was added to the reaction system (entry 16). As a
result, the optimal reaction condition was determined as below: CPME as the reaction solvent, 4Å
molecular sieve as the additive, the HDA reaction being carried out under catalysis of a facile
copper complex at -25°C.
a
Table 1. Optimization of the reaction conditions
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entry ligand
solvent
EtOAc
T ( C) yield (%) ee (%)
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L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L1
L2
L4
L3
L3
L3
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-15
79
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89
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86
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69
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80
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95
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2
Toluene -15
3
CH Cl
-15
-15
-15
-15
-15
-15
-20
-25
-30
-35
-25
-25
-25
-25
-25
-25
2
2
4
CHCl3
5
MTBE
THF
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7
Et O
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CPME
CPME
CPME
CPME
CPME
CPME
CPME
CPME
CPME
CPME
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d
e
f
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a
Unless otherwise noted, all reactions were performed with 1a (0.1 mmol), 2a (0.2 mmol), L (10
b
c
mol%), Et N (10 mol%) and Cu(OTf) (10 mol%). Isolated yield. Determined by chiral HPLC
3
2
d
e
analysis. Addition of 50 mg of powder 4Å molecular sieve. Addition of 50 mg of Na SO .
2
4
f
Addition of 50 mg of MgSO . Tf = trifluoromethanesulfonyl. MTBE = Methyl tert-butyl ether.
4
CPME = Cyclopentyl methyl ether.
With the optimal conditions in hand, the substrate scope of 2-oxo-2-phenylacetaldehyde hydrate
was examined, as shown in Table 2. Firstly, the electronic effect of the substrates was investigated.
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When the substrates bearing the strong electron-donating groups on the para-position of the
phenyl ring were employed, the HDA reactions could be carried out smoothly to give the desired
products with high yields and excellent enantioselectivities (3e, 3g). Similarly, the
electron-withdrawing halogen groups were compatible with the reaction system (3b, 3c, 3d). The
HDA adduct 3f was obtained with good yield and excellent enantiselectivity when the strong
electron-withdrawing trifluoromethyl group was on the para-position of the phenyl ring. It was
obvious that the substrates with the electron-donating groups could give higher yields than those
with the electron-withdrawing groups. Then, the steric effect of the reaction was examined. The
results showed that substitutions at different positions on the phenyl group had little influence on
the reaction yields and enantioselectivities (3e, 3j, 3k). In the case of heterocyclic product 3l,
2-thienyl-dihydropyrone, a satisfactory result could be obtained by simply lowering the reaction
temperature to -35°C. The substrates bearing 2-naphthyl group and multisubstituted group could
also give the corresponding products with high yields and enantioselectivities, respectively
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1
(3m-3o). Notably, when the R group was changed to the aliphatic group, the desired product 3p
was still obtained in moderate yield and excellent enantioselectivity. The absolute configuration of
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the product 3d was confirmed by X-ray crystal diffraction.
a,b,c
Table 2. Scope of glyoxals
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a
Unless otherwise noted, the reaction of 1 (0.3 mmol) and 2a (0.6 mmol) was performed in the
presence of L3 (10 mol%), Et N (10 mol%) and Cu(OTf) (10 mol%) in CPME (3.0 mL) with 150
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mg of powder 4Å molecular sieve as additive at -25 °C. Isolated yield. Determined by chiral
d
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HPLC analysis. In MTBE (3.0 mL) at -35 C.
A variety of dihydropyrones were obtained with good yields and enantioselectivities through the
catalysis of the copper complex. Next, we wondered whether the catalytic system could promote
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the asymmetric HDA reaction of isatins. Pleasingly, when isatins were evaluated in this reaction,
the desired products 5a and 5b could be obtained with high yields and excellent
enantioselectivities under this catalytic system (Scheme 2). And 5b was a known compound, the
absolute configuration of 5b was determined by comparison with corresponding specific rotation
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8e
data reported in literature.
a,b,c
Scheme 2. Scope of Isatins
a
Unless otherwise noted, the reactions of 4 (0.3mmol) and 2a (0.6mmol) were performed in the
presence of L3 (10 mol%), Et N (10 mol%), Cu(OTf) (10 mol%), R= CH in MTBE (3.0 mL)
3
2
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b
c
and R= Bn in Toluene (3.0 mL) at -10 °C. Isolated yields. Determined by chiral HPLC analysis.
To further demonstrate the robust nature and operational simplicity of this methodology, a gram
scale experiment was carried out (Scheme 3). The copper complex of 5% catalytic loading could
catalyze the HDA reaction of 1e and Danishefsky’s diene to generate the desired product 3e with
1.69g quantity, 78% yield and 90% ee.
a,b,c
Scheme 3. Asymmetric Hetero-Diels-Alder Reaction on a gram scale
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The reaction of 1e (10 mmol) and 2a (20 mmol) was performed in the presence of L3 (5 mol%),
Et N (5 mol%) and Cu(OTf) (5 mol%) in CPME (18 mL) with 2.5g of powder 4Å molecular
3
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sieve as additive at -25 °C. Isolated yield. Determined by chiral HPLC analysis.
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Finally, the reaction mechanism was studied. Generally, two possible reaction pathways,
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Diels-Alder cycloaddition and stepwise Mukaiyama-aldol condensation, were involved in this
transformation. As shown in Scheme 4, in this reaction, 2-oxo-2-phenylacetaldehyde hydrate
gradually released the phenylglyoxal 7 when 4Å molecular sieve was added in the reaction
1
4
system. With this strategy, the in situ generated phenylglyoxal immediately reacted with
’
Danishefsky s diene in the presence of the chiral copper catalyst.
In order to get insight into the reaction mechanism, several control experiments were carried out
’
(
Scheme 4). For the HDA reaction of Danishefsky s diene 2a with 1e, the intermediate 8 was
isolated before the treatment of TFA. The NMR spectral experiment of the intermediate 8 showed
that the Mukaiyama-aldol adduct was produced under the reaction condition, corresponding to the
stepwise pathway. As expected, the ee vaule of the Mukaiyama-aldol adduct was well consistent
with that of final product, which indicated that TFA acidification had no influence on the
’
stereocontrol. However, when the TMS group of Danishefsky s diene was changed to a TBS group,
only the cycloaddition adduct 9, which was confirmed by NMR, was isolated by silica gel
chromatography. This cycloaddition intermediate could be easily transferred into the final product
by the treatment of TFA. Similarly, the ee value was maintained after TFA acidification. In view
of the experimental results above, the different reaction pathways involved in this reaction were
greatly dependent on the substrate dienes.
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Scheme 4. The mechanism pathway of the Hetero-Diels-Alder Reaction
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’
In summary, a copper catalyzed asymmetric hetero-Diels-Alder reaction of Danishefsky s diene
with glyoxals was developed under mild reaction conditions. With this efficient methodogy, an
unprecedented substrate scope was achieved and a variety of dihydropyranones were provided
with excellent enantioselectivities and high yields. Moreover, a detailed reaction mechanism study
showed that a substrate-dependent pathway, stepwise Mukaiyama-aldol condensation and
concerted cycloaddition, was involved in this reaction.
Experiment Section
1
13
General Information: H NMR and C NMR were recorded on a 400MHz Nuclear Magnetic
1
13
Resonance Spectrometer ( H NMR: 400MHz, C NMR: 100MHz) using TMS as internal
reference. The chemical shifts (δ) and coupling constants (J) were expressed in ppm and Hz,
respectively. UV-Vis Spectrophotometry was carried out on infrared spectrometer. HPLC analysis
was carried out on HPLC with a multiple wavelength detector by commercial chiral columns.
Optical rotations were measured on a Polarimeter. HRMS (ESI) were recorded on a Q-TOF
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Premier. Commercially available compounds were used without further purification. Solvents
10a, 10c
were purified according to the standard procedures unless otherwise noted. Ligands
, various
14a
10d
15
16
glyoxals , N-methyl isatins , N-benzyl isatins , and Danishefsky’s diene were prepared
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according to literature procedures.
General procedures of Hetero-Diels-Alder reaction: A mixture of Ligand (L3, 10 mol %),
Cu(OTf) (10 %, 10.8 mg) and Et N (10 %, 4.17 μL) in corresponding solvent (3.0 mL) was
2
3
stirred for 1h at ambient atmosphere, corresponding glyoxals (0.3 mmol) and 150 mg of powder
4Å molecular sieve as additive were then added. The resulting mixture was cooled to -25 °C .
After 30min, corresponding diene was added slowly by syringe. After reactions were finished
(monitored by TLC), 5.0 equiv. TFA was added to quench the reaction. The system was quenched
by saturated sodium bicarbonate after 2h and then extracted by ethyl acetate. The organic phase
was dried with sodium sulfate, evaporated in vacuo. Purification by column chromatograph
afforded HDA adducts.
Experimental data of HDA adducts
(R)-2-benzoyl-2H-pyran-4(3H)-one (3a):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow solid: 86% yield; mp = 127-129 °C; [α]D -156.7 (c = 0.84, CHCl , 95% ee); HPLC:
3
Daicel Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 0.8 mL/min, T = 23°C, UV =
1
254 nm, t = 10.56 min (major), t = 29.09 min (minor); H NMR (400 MHz, CDCl ): δ 7.96 (d, J
R
R
3
=
7.3 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.8 Hz, 2H), 7.40 (d, J = 6.1 Hz, 1H), 5.81 (dd,
J = 11.4 Hz, 4.6 Hz, 1H), 5.49 (d, J = 6.04 Hz, 1H), 2.96 (dd, J = 17.1 Hz, 11.5 Hz, 1H), 2.80 (dd,
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J = 17.0 Hz, 4.5 Hz, 1H); C NMR (100 MHz, CDCl ): δ 193.1, 190.0, 161.7, 134.3, 133.7,
3
-1
1
1
29.00, 128.99, 107.9, 78.9, 38.0; IR (film, ν/cm ): 3687, 2923, 2856, 2364, 1959, 1751, 1461,
＋
263, 1068, 802, 682; HRMS (ESI) m/z calcd for C H O [M+Na] 225.0528, found 225.0523.
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(
R)-2-(4-fluorobenzoyl)-2H-pyran-4(3H)-one (3b):
The title compound was prepared according to the general working procedure (20h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow solid: 77% yield; mp = 146-148 °C; [α]D -172.9 (c = 0.84, CHCl , 91% ee); HPLC:
3
Daicel Chiralpak OD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV =
1
2
54 nm, t = 10.12 min (mionr), t = 11.75 min (major); H NMR (400 MHz, CDCl ): δ 8.02 (dd,
R
R
3
J = 8.6 Hz, 5.4 Hz, 2H), 7.38 (d, J = 6.0 Hz, 1H), 7.18 (t, J = 8.5 Hz, 2H), 5.75 (dd, J = 11.2 Hz,
4.4 Hz, 1H), 5.50 (d, J = 6.0 Hz, 1H), 2.98 (dd, J = 17.0 Hz, 11.3 Hz, 1H), 2.79 (dd, J = 17.0 Hz,
13
1
4
1
.4 Hz, 1H); C NMR (100 MHz, CDCl ): δ 191.6, 190.0, 166.3 ( J = 255.9 Hz, 1C), 161.4,
3 CF
3
4
2
31.9 ( J = 9.5 Hz, 2C), 130.2 ( J = 2.9 Hz, 1C), 116.2 ( J = 21.9 Hz, 2C), 108.0, 78.8, 37.8;
CF
CF
CF
-1
IR (film, ν/cm ):3781, 3706, 3461, 2923, 2856, 1689, 1514, 1461, 1375, 1270, 1222, 1031, 859,
＋
7
43, 601; HRMS (ESI) m/z calcd for C H FO [M+Na] 243.0433, found 243.0432.
12 9 3
(R)-2-(4-chlorobenzoyl)-2H-pyran-4(3H)-one (3c):
The title compound was prepared according to the general working procedure (20h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
20
yellow solid: 84% yield; mp = 96-98 °C; [α]D -149.9 (c = 1.02, CHCl , 94% ee); HPLC: Daicel
3
Chiralpak OD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm,
1
t = 10.59 min (minor), t = 12.28 min (major); H NMR (400 MHz, CDCl ): δ 7.91 (d, J = 8.5 Hz,
R
R
3
2
H), 7.47 (d, J = 8.5 Hz, 2H), 7.37 (d, J = 6.0 Hz, 1H), 5.73 (dd, J = 11.1 Hz, 4.6 Hz, 1H), 5.49 (d,
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J = 6.0 Hz, 1H), 2.96 (dd, J = 17.0 Hz, 11.2 Hz, 1H), 2.79 (dd, J = 17.0 Hz, 4.5 Hz, 1H); C NMR
(
100 MHz, CDCl ): δ 191.0, 188.8, 160.3, 139.8, 131.0, 129.5, 128.3, 107.0, 77.8, 36.7; IR (film,
3
-1
ν/cm ): 3766, 3704, 3459, 2923, 2856, 2370, 1679, 1592, 1452, 1398, 1085, 802, 609; HRMS
0
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7
8
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0
＋
(
ESI) m/z calcd for C H ClO [M+Na] 259.0138, found 259.0132.
12 9 3
(R)-2-(4-bromobenzoyl)-2H-pyran-4(3H)-one (3d):
The title compound was prepared according to the general working procedure (20h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow solid: 85% yield; mp = 107-109 °C; [α]D -129.2 (c = 0.52, CHCl , 94% ee); HPLC:
3
Daicel Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 0.8 mL/min, T = 23°C, UV =
1
2
54 nm, t = 11.71 min (major), t = 24.21 min (minor); H NMR (400 MHz, CDCl ): δ 7.84 (d, J
R
R
3
= 8.6 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.38 (d, J = 6.0 Hz, 1H), 5.73 (dd, J = 11.1 Hz, 4.6 Hz,
1
1
H), 5.50 (d, J = 6.0 Hz, 1H), 2.97 (dd, J = 17.0 Hz, 11.1 Hz, 1H), 2.80 (dd, J = 17.0 Hz, 4.5 Hz,
1
3
H); C NMR (100 MHz, CDCl ): δ 192.3, 189.9, 161.4, 132.4, 132.3, 130.5, 129.7, 108.1, 78.8,
3
-1
37.7; IR (film, ν/cm ): 3714, 2921, 2856, 1677, 1591, 1459, 1398, 1068, 935, 802, 732, 615;
＋
HRMS (ESI) m/z calcd for C H BrO [M+Na] 302.9633, found 302.9629.
12
19
3
(R)-2-(4-methylbenzoyl)-2H-pyran-4(3H)-one (3e):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
20
yellow solid: 84% yield; mp = 89-91 °C; [α]D -123.3 (c = 0.94, CHCl , 96% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 0.8 mL/min, T = 23°C, UV = 254 nm, tR
1
=
11.05 min (major), t = 19.61 min (minor); H NMR (400 MHz, CDCl ): δ7.85 (d, J = 8.3 Hz,
R
3
2
H), 7.39 (d, J = 6.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 5.78 (dd, J = 11.6 Hz, 4.6 Hz, 1H), 5.48
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dd, J = 6.0 Hz, 0.8 Hz, 1H), 2.95 (dd, J = 17.1 Hz, 11.7 Hz, 1H), 2.78 (ddd, J = 17.0 Hz, 4.5 Hz,
13
0
1
1
.9 Hz, 1H), 2.42 (s, 3H); C NMR (100 MHz, CDCl ): δ 192.6, 190.2, 161.7, 145.5, 131.2, 129.7,
3
-1
29.1, 107.8, 78.9, 38.1, 21.8; IR (film, ν/cm ): 3781, 2923, 2856, 1679, 1596, 1452, 1403, 1277,
10
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60
＋
037, 935, 798, 599; HRMS (ESI) m/z calcd for C H O [M+Na] 239.0684, found 239.0684.
1
3
12
3
(R)-2-(4-(trifluoromethyl)benzoyl)-2H-pyran-4(3H)-one (3f):
The title compound was prepared according to the general working procedure (21h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow oil: 71% yield; [α]D -109.3 (c = 0.68, CHCl , 90% ee); HPLC: Daicel Chiralpak OD-H,
3
hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, t = 9.24 min
R
1
(minor), t = 10.40 min (major); H NMR (400 MHz, CDCl ): δ 8.10 (d, J = 8.2 Hz, 2H), 7.79 (d,
R
3
J = 8.2 Hz, 2H), 7.38 (d, J = 6.1 Hz, 1H), 5.77 (dd, J = 10.8 Hz, 4.6 Hz, 1H), 5.53 (d, J = 6.0 Hz,
1
3
1
H), 3.01 (dd, J = 17.0 Hz, 10.8 Hz, 1H), 2.85 (dd, J = 17.1 Hz, 4.5 Hz, 1H); C NMR (100 MHz,
2
4
CDCl ): δ 191.6, 188.7, 160.2, 135.5, 134.3 (q, J = 32.8 Hz, 1C), 128.5, 125.0 (q, J = 3.6 Hz,
3
CF
CF
1
-1
2C), 122.3 (q, J = 271.2 Hz, 1C), 107.2, 77.9, 36.5; IR (film, ν/cm ): 3704, 3363, 2923, 2856,
CF
2
724, 2279, 1936, 1697, 1598, 1457, 1332, 1267, 1135, 1068, 1025, 966, 856, 804, 727, 597;
＋
HRMS (ESI) m/z calcd for C H F O [M+Na] 293.0401, found 293.0401.
13
9
3
3
(R)-2-(4-methoxybenzoyl)-2H-pyran-4(3H)-one (3g):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow solid: 96% yield; mp = 122-124 °C; [α]D -116.9 (c = 1.10, CHCl , 94% ee); HPLC:
3
Daicel Chiralpak OD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV =
1
2
54 nm, t = 12.99 min (minor), t = 14.51 min (major); H NMR (400 MHz, CDCl ): δ 7.95 (d, J
R
R
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=
9.2 Hz, 2H), 7.39 (d, J = 6.0 Hz, 1H), 6.96 (d, J = 8.8 Hz, 2H), 5.76 (dd, J = 11.8 Hz, 4.4 Hz,
1H), 5.48 (d, J = 6.0 Hz, 1H), 3.88 (s, 3H), 2.96 (dd, J = 17.0 Hz, 11.8 Hz, 1H), 2.76 (dd, J = 17.0
13
Hz, 4.3 Hz, 1H); C NMR (100 MHz, CDCl ): δ 191.3, 190.3, 164.4, 161.7, 131.4, 126.6, 114.2,
3
0
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7
8
9
0
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7
8
9
0
-1
107.8, 78.8, 55.6, 38.2; IR (film, ν/cm ): 3781, 2923, 2856, 2724, 1747, 1681, 1598, 1457, 1375,
＋
1261, 1168, 1091, 1027, 804, 599; HRMS (ESI) m/z calcd for C H O [M+Na] 255.0633,
1
3
12
4
found 255.0639.
(R)-2-(3-methoxybenzoyl)-2H-pyran-4(3H)-one (3h):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow oil: 90% yield; mp = 71-73 °C; [α]D -115.3 (c = 0.86, CHCl , 92% ee); HPLC: Daicel
3
Chiralpak OD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 240 nm,
1
t = 12.03 min (major), t = 13.77 min (minor); H NMR (400 MHz, CDCl ): δ 7.51-7.38 (m, 4H),
R
R
3
7.17-7.15 (m, 1H), 5.79 (dd, J = 11.4 Hz, 4.6 Hz, 1H), 5.48 (d, J = 6.0 Hz, 1H), 3.84 (s, 3H), 2.94
1
3
(dd, J = 17.0 Hz, 11.4 Hz, 1H), 2.79 (dd, J = 17.0 Hz, 4.6 Hz, 1H); C NMR (100 MHz, CDCl ):
3
δ 191.9, 189.0, 160.7, 159.0, 133.9, 128.9, 120.4, 119.7, 112.3, 106.8, 77.9, 54.5, 37.0; IR (film,
-1
ν/cm ): 3704, 3363, 2923, 2856, 2726, 2364, 2067, 1936, 1687, 1594, 1457, 1375, 1265, 1203,
＋
1033, 873, 798; HRMS (ESI) m/z calcd for C H O [M+Na] 255.0633, found 255.0634.
1
3
12
4
(R)-2-(3-chlorobenzoyl)-2H-pyran-4(3H)-one (3i):
The title compound was prepared according to the general working procedure (19h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
20
yellow oil: 87% yield; mp = 115-117 °C; [α]D -118.6 (c = 1.02, CHCl , 91% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, tR
1
=
=
8.28 min (major), t = 16.44 min (minor); H NMR (400 MHz, CDCl ): δ 7.93 (s, 1H), 7.84 (d, J
R
3
7.8 Hz, 1H), 7.61-7.59 (m, 1H), 7.45 (t, J = 7.9 Hz, 1H), 7.39 (d, J = 6.0 Hz, 1H), 5.74 (dd, J =
1.0 Hz, 4.6 Hz, 1H), 5.50 (d, J = 6.0 Hz, 1H), 2.96 (dd, J = 17.0 Hz, 11.0 Hz, 1H), 2.81 (dd, J =
1
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7.0 Hz, 4.5 Hz, 1H); C NMR (100 MHz, CDCl ): δ 192.1, 189.9, 161.5, 135.31, 135.25, 134.2,
3
-1
30.3, 129.1, 127.2, 108.1, 78.8, 37.7; IR (film, ν/cm ): 3781, 3704, 2923, 2856, 2726, 1687,
＋
596, 1459, 1267, 1085, 946, 798, 728, 630; HRMS (ESI) m/z calcd for C H ClO [M+Na]
1
2
9
3
10
11
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13
14
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59.0138, found 259.0144.
(R)-2-(3-methylbenzoyl)-2H-pyran-4(3H)-one (3j):
The title compound was prepared according to the general working procedure (17h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow oil: 92% yield; [α]D -124.4 (c = 0.98, CHCl , 94% ee); HPLC: Daicel Chiralpak AD-H,
3
hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, t = 8.04 min
R
1
(
major), t = 17.75 min (minor); H NMR (400 MHz, CDCl ): δ 7.74 (d, J = 8.4 Hz, 2H),
R
3
7.45-7.37 (m, 3H), 5.81 (dd, J = 11.6 Hz, 4.6 Hz, 1H), 5.50 (d, J = 6.0 Hz, 1H), 2.95 (dd, J = 17.0
1
3
Hz, 11.6 Hz, 1H), 2.79 (dd, J = 17.0 Hz, 4.4 Hz, 1H), 2.42(s, 3H); C NMR (100 MHz, CDCl ): δ
3
1
93.3, 190.0, 161.7, 138.9, 135.1, 133.8, 129.4, 128.8, 126.1, 107.8, 78.9, 38.1, 21.3; IR (film,
-1
ν/cm ): 3704, 3627, 3459, 3359, 3187, 2923, 2856, 2732, 2630, 2443, 2258, 2069, 1903, 1685,
＋
1
2
594, 1457, 1376, 1160, 1033, 952, 875, 796, 736; HRMS (ESI) m/z calcd for C H O [M+Na]
13 12 3
39.0684, found 239.0687.
(R)-2-(2-methylbenzoyl)-2H-pyran-4(3H)-one (3k):
The title compound was prepared according to the general working procedure (24h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow oil: 85% yield; mp = 95-97 °C; [α]D -155.1 (c = 0.82, CHCl , 90% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, tR
1
=
8.65 min (major), t = 19.02 min (minor); H NMR (400 MHz, CDCl ): δ 7.56 (d, J = 7.9 Hz,
R
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H), 7.45-7.40 (m, 1H), 7.35 (d, J = 6.1 Hz, 1H), 7.30 (s, 1H), 7.28 (s, 1H), 5.67 (dd, J = 10.5 Hz,
.0 Hz, 1H), 5.46 (dd, J = 6.1 Hz, 0.4 Hz, 1H), 2.89 (dd, J = 17.0 Hz, 10.4 Hz, 1H), 2.78 (ddd, J =
13
7.0 Hz, 5.0 Hz, 0.6 Hz, 1H), 2.45(s, 3H); C NMR (100 MHz, CDCl ): δ 197.4, 189.9, 161.7,
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
8
9
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7
8
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7
8
9
0
-1
39.3, 134.3, 132.3, 132.2, 128.5, 125.7, 108.0, 80.1, 37.7, 20.9; IR (film, ν/cm ): 3781, 3704,
3459, 2923, 2856, 1679, 1594, 1454, 1403, 1272, 1066, 804, 736, 607; HRMS (ESI) m/z calcd for
＋
C H O [M+Na] 239.0684, found 239.0682.
1
3
12
3
(R)-2-(thiophene-2-carbonyl)-2H-pyran-4(3H)-one (3l):
The title compound was prepared according to the general working procedure (19h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow solid: 80% yield; mp = 81-82 °C; [α]D -136.4 (c = 0.74, CHCl , 90% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 240 nm, tR
1
=
9.70 min (major), t = 22.76 min (minor); H NMR (400 MHz, CDCl ): δ 7.91 (d, J = 3.6 Hz,
R
3
1
H), 7.76 (d, J = 4.8 Hz, 1H), 7.42 (d, J = 6.0 Hz, 1H), 7.18 (t, J = 4.4 Hz, 1H), 5.55 (dd, J = 11.8
Hz, 4.4 Hz, 1H), 5.50 (d, J = 6.0 Hz, 1H), 2.99 (dd, J = 17.0 Hz, 11.8 Hz, 1H), 2.80 (dd, J = 17.0
13
Hz, 4.4 Hz, 1H); C NMR (100 MHz, CDCl ): δ 189.9, 186.2, 161.4, 140.0, 135.8, 134.2, 128.6,
3
-1
1
08.1, 80.1, 38.3; IR (film, ν/cm ): 2923, 2856, 2726, 2364, 1751, 1675, 1594, 1459, 1375, 1265,
＋
1218, 908, 802, 727; HRMS (ESI) m/z calcd for C H SO [M+Na] 231.0092, found 231.0094.
1
0
8
3
(R)-2-(3,4-difluorobenzoyl)-2H-pyran-4(3H)-one (3m):
The title compound was prepared according to the general working procedure (20h) and purified
by column chromatography (petroleum ether / ethyl acetate = 2:1) to give the product as a light
2
0
yellow oil: 85% yield; [α]D -140.4 (c = 1.06, CHCl , 92% ee); HPLC: Daicel Chiralpak AD-H,
3
hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, t = 7.77 min
R
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(
major), t = 21.33 min (minor); H NMR (400 MHz, CDCl ): δ 7.87-7.77 (m, 2H), 7.37 (d, J =
R
3
6
6
.0 Hz, 1H), 7.30 (dd, J = 17.1 Hz, 8.7 Hz, 1H), 5.70 (dd, J = 10.9 Hz, 4.6 Hz, 1H), 5.50 (d, J =
13
.0 Hz, 1H), 2.98 (dd, J = 17.1 Hz, 11.0 Hz, 1H), 2.80 (dd, J = 17.0 Hz, 4.5 Hz, 1H); C NMR
10
11
12
13
14
15
16
17
18
19
20
21
22
23
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26
27
28
29
30
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
1
2
(
100 MHz, CDCl ): δ 190.8, 189.8, 161.2, 154.3 (dd, J = 258.0 Hz, J = 13.2 Hz, 1C), 150.6
3 CF CF
1
2
3
4
(dd, J = 250.5 Hz, J = 12.8 Hz, 1C), 130.8 (dd, J = 4.4 Hz, J = 3.7 Hz, 1C), 126.4 (dd,
CF
CF
CF
CF
3
4
3
4
JCF = 8.0 Hz, J = 3.6 Hz, 1C), 118.7 (dd, J = 18.2 Hz, J = 2.1 Hz, 1C), 118.0 (d, J=17.7
CF
CF
CF
-1
Hz, 1C), 108.2, 78.8, 37.6; IR (film, ν/cm ): 3781, 3706, 3461, 3072, 2923, 2856, 1683, 1598,
＋
1513, 1459, 1270, 1033, 894, 802, 607; HRMS (ESI) m/z calcd for C H F O [M+Na]
1
2
8
2
3
2
61.0339, found 261.0346.
(
R)-2-(benzo[d][1,3]dioxole-5-carbonyl)-2H-pyran-4(3H)-one (3n):
The title compound was prepared according to the general working procedure (19h) and purified
by column chromatography (petroleum ether / ethyl acetate = 2:1) to give the product as a light
2
0
yellow solid: 65% yield; mp = 123-125 °C [α]D -125.5 (c = 0.58, CHCl , 93% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 254 nm, tR
1
=
13.26 min (major), t = 25.28 min (minor); H NMR (400 MHz, CDCl ): δ 7.59 (dd, J = 8.2 Hz,
R
3
1
.6 Hz, 1H), 7.45 (d, J = 1.6 Hz, 1H), 7.41 (d, J = 6.0 Hz, 1H), 6.90 (d, J = 8.2 Hz, 1H), 6.09 (s,
2H), 5.72 (dd, J = 11.8 Hz, 4.4 Hz, 1H), 5.51 (d, J = 6.0 Hz, 1H), 2.98 (dd, J = 17.0 Hz, 11.8 Hz,
1
3
1
H), 2.77 (dd, J = 17.1 Hz, 4.4 Hz, 1H); C NMR (100 MHz, CDCl ): δ 190.9, 190.2, 161.6,
3
-1
1
52.8, 148.5, 128.4, 125.7, 108.6, 108.2, 107.9, 102.2, 78.7, 38.2; IR (film, ν/cm ): 3781, 3714,
3461, 2923, 2856, 1679, 1594, 1452, 1398, 1259, 1072, 802, 613; HRMS (ESI) m/z calcd for
＋
C H O [M+Na] 269.0426, found 269.0429.
1
3
10
5
(R)-2-(2-naphthoyl)-2H-pyran-4(3H)-one (3o):
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The title compound was prepared according to the general working procedure (19h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
20
yellow oil: 92% yield; [α]D -69.3 (c = 1.00, CHCl , 93% ee); HPLC: Daicel Chiralpak OD-H,
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hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 240 nm, t = 14.65 min
R
1
(major), t = 24.44 min (minor); H NMR (400 MHz, CDCl ): δ 8.50 (s, 1H), 8.02-7.89 (m, 4H),
R
3
7
1
.67-7.57 (m, 2H), 7.44 (d, J = 6.0 Hz, 1H), 5.97 (dd, J = 11.6 Hz, 4.5 Hz, 1H), 5.54 (d, J = 6.0 Hz,
1
3
H), 3.04 (dd, J = 17.0 Hz, 11.6 Hz, 1H), 2.87 (dd, J = 17.0 Hz, 4.3 Hz, 1H); C NMR (100 MHz,
CDCl ): δ 193.0, 190.2, 161.7, 136.0, 132.4, 131.1, 131.0, 129.8, 129.3, 129.0, 127.9, 127.2, 124.1,
3
-1
1
08.0, 79.0, 38.2; IR (film, ν/cm ): 3781, 3461, 3060, 2923, 2856, 2726, 2364, 1955, 1681, 1594,
1
459, 1376, 1265, 1182, 1093, 1027, 809, 873, 584; HRMS (ESI) m/z calcd for C H O [M+Na]
1
6
12
3
＋
275.0684, found 275.0685.
(R)-2-(cyclohexanecarbonyl)-2H-pyran-4(3H)-one (3p):
The title compound was prepared according to the general working procedure (24h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a light
2
0
yellow oil: 61% yield; [α]D -41.9 (c = 0.44, CHCl , 90% ee); HPLC: Daicel Chiralpak AD-H,
3
hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 254 nm, t = 5.75 min
R
1
(major), t = 8.96 min (minor); H NMR (400 MHz, CDCl ): δ 7.40 (d, J = 6.0 Hz, 1H), 5.47 (d, J
R
3
=
6.0 Hz, 1H), 4.95 (dd, J = 11.0 Hz, 5.9 Hz, 1H), 2.85-2.78 (m, 1H), 2.75-2.71 (m, 2H),
13
1
.88-1.67 (m, 5H), 1.41-1.20 (m, 5H); C NMR (100 MHz, CDCl ): δ 208.1, 190.2, 161.7, 108.1,
3
-1
80.9, 46.3, 37.6, 28.4, 28.0, 25.6, 25.57, 25.4; IR (film, ν/cm ): 3781, 3714, 2923, 2856, 2387,
＋
452, 1375, 1068, 800, 721, 609; HRMS (ESI) m/z calcd for C H O [M+Na] 231.0997, found
1
2
12 16 3
31.1000.
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(
R)-1-methylspiro[indoline-3,2'-pyran]-2,4'(3'H)-dione (5a):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a white
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2
0
solid: 93% yield; mp = 106-108 °C; [α]D +363.9 (c = 1.08, CHCl , 91% ee); HPLC: Daicel
3
Chiralpak AD-H, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 240 nm, tR
1
=
9.09 min (major), t = 11.95 min (minor); H NMR (400 MHz, CDCl ): δ7.47 (ddd, J = 7.5 Hz,
R
3
1
.2 Hz, 0.5 Hz, 1H), 7.41-7.37 (m, 2H), 7.07-7.03 (m, 1H), 6.87 (d, J = 7.9 Hz, 1H), 5.60 (dd, J =
6.2 Hz, 0.8 Hz, 1H), 3.21 (s, 3H), 3.18 (d, J = 16.6 Hz, 1H), 2.64 (dd, J = 16.6 Hz, 0.8 Hz, 1H);
1
3
C NMR (100 MHz, CDCl ): δ 189.3, 171.9, 161.4, 143.0, 131.3, 127.5, 124.3, 123.6, 109.1,
3
-1
1
07.0, 81.4, 41.3, 26.5; IR (film, ν/cm ): 3781, 2923, 2856, 1727, 1679, 1604, 1461, 1375, 1093,
＋
1029, 904, 800, 607; HRMS (ESI) m/z calcd for C H NO [M+Na] 252.0637, found 252.0639.
1
3
11
3
(
R)-1-benzylspiro[indoline-3,2'-pyran]-2,4'(3'H)-dione (5b):
The title compound was prepared according to the general working procedure (16h) and purified
by column chromatography (petroleum ether / ethyl acetate = 3:1) to give the product as a white
2
0
solid: 96% yield; mp = 106-108 °C [α]D +186.3 (-191.7, reported) (c = 0.30, CH Cl , 91% ee);
2
2
HPLC: Daicel Chiralpak ID, hexane: 2-propanol = 70:30, flow rate = 1.0 mL/min, T = 23°C, UV
= 254 nm, t = 24.36 min (minor), t = 34.95 min (major), [HPLC: Daicel Chiralpak ID, hexane:
R
R
2
-propanol = 70:30,flow rate = 1.0 mL/min, UV = 254 nm, t = 21.15 min (major), t = 29.10 min
r1 r2
1
(
minor), reported]; H NMR (400 MHz, CDCl ): δ 7.50-7.48 (m, 1H), 7.42 (d, J = 6.2 Hz, 1H),
3
7.35-7.31 (m, 2H), 7.29-7.24 (m, 4H), 7.04-7.00 (m, 1H), 6.76 (d, J = 7.9 Hz, 1H), 5.64 (dd, J =
6
1
.2 Hz, 0.7 Hz, 1H), 4.93 (d, J = 15.6 Hz, 1H), 4.85(1H, J = 15.6 Hz, 1H), 3.25 (d, J = 16.6 Hz,
13
H), 2.73 (dd, J = 16.6 Hz, 0.7 Hz, 1H); C NMR (100 MHz, CDCl ): δ 189.2, 172.2, 161.4,
3
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42.1, 134.8, 131.2, 129.0, 128.0, 127.5, 127.2, 124.4, 123.6, 110.1, 107.0, 81.4, 44.0, 41.4; IR
-1
(film, ν/cm ): 3459, 2923, 2856, 2724, 1733, 1702, 1669, 1459, 1375, 1265, 1155, 802, 730, 613;
＋
HRMS (ESI) m/z calcd for C H NO [M+Na] 328.0950, found 328.0944.
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(R)-2-hydroxy-6-methoxy-1-p-tolylhex-5-ene-1,4-dione (8):
The title compound was prepared according to the general working procedure and purified by
column chromatography (dichloromethane / ethyl acetate = 8:1) to give the product as a colorless
2
0
oil. [α]D +5.7 (c = 0.33, CHCl , 96% ee); HPLC: Daicel Chiralpak AD-H, hexane: 2-propanol =
3
70:30, flow rate = 1.0 mL/min, T = 23°C, UV = 230 nm, t = 10.93 min (minor), t = 12.01 min
R
R
1
(major); H NMR (400 MHz, CD COCD ): δ 7.92 (d, J = 8.2 Hz, 2H), 7.68 (d, J = 12.7 Hz, 1H),
3 3
7.35 (d, J = 8.0 Hz, 2H), 5.69 (d, J = 12.8 Hz, 1H), 5.45 (dd, J = 7.2 Hz, 4.4 Hz, 1H), 3.76 (s, 3H),
1
2.98 (dd, J = 16.4 Hz, 4.4 Hz, 1H), 2.87 (dd, J = 16.3 Hz, 7.2 Hz, 1H), 2.41 (s, 3H); [ H NMR
(400 MHz, (CD ) SO): δ 7.87 (d, J = 8.2 Hz, 2H), 7.71 (d, J = 12.7 Hz, 1H), 7.33 (d, J = 8.0 Hz,
3 2
2H), 5.65 (d, J = 12.8 Hz, 1H), 5.52 (d, J = 7.2 Hz, 1H), 5.29 (dd, J = 12.8 Hz, 6.7 Hz, 1H), 3.70
1
3
(s, 3H), 2.93 (dd, J = 16.3 Hz, 5.7 Hz, 1H), 2.81 (dd, J = 16.3 Hz, 6.9 Hz, 1H), 2.38 (s, 3H)]; C
NMR (100 MHz, CD COCD ): δ 200.4, 196.6, 164.3, 145.0, 133.2, 130.2, 129.7, 107.1, 70.7,
3
3
-1
58.3, 45.8, 21.6; IR (film, ν/cm ): 3687, 3459, 2923, 2856, 2726, 2281, 1745, 1679, 1594, 1459,
＋
1176, 1089, 808, 728, 599, 522; HRMS (ESI) m/z calcd for C H O [M+Na] 271.0946, found
1
4
16
4
271.0945.
(R)-4-(tert-butyldimethylsilyloxy)-6-methoxy-3,6-dihydro-2H-pyran-2-yl)(p-tolyl)methanone
(9):
The title compound was prepared according to the general working procedure and purified by
column chromatography (dichloromethane / ethyl acetate = 10:1) to give the product as a colorless
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oil. [α]D -7.5 (c = 0.78, CHCl , 93% ee); HPLC: Daicel Chiralpak AD-H, hexane: 2-propanol =
3
7
0:30, flow rate = 0.7 mL/min, T = 23°C, UV = 230 nm, t = 5.61 min (major), t = 6.01 min
R R
1
(
minor); H NMR (400 MHz, CD COCD ): δ 7.95 (d, J = 8.2 Hz, 2H), 7.38-7.36 (m, 2H), 5.30
3 3
10
11
12
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(
ddd, J = 11.2 Hz, 3.7 Hz, 0.6 Hz, 1H), 5.07-5.06 (m, 1H), 4.95 (dd, J = 3.2 Hz, 2.0 Hz, 1H), 3.45
(s, 3H), 2.63-2.55 (m, 1H), 2.42 (s, 3H), 2.10-2.04 (m, 1H), 0.95 (s, 9H), 0.23 (s, 3H), 0.22 (s, 3H);
13
C NMR (100 MHz, CD COCD ): δ 195.3, 152.2, 144.0, 133.1, 129.1, 102.5, 98.2, 68.1, 55.3,
3
3
-1
3
0.7, 25.1, 20.8, 17.7, -5.1, -5.4; IR (film, ν/cm ): 3775, 3704, 3459, 3189, 2925, 2856, 2726,
1743, 1672, 1606, 1459, 1373, 1263, 1211, 1126, 1056, 950, 898, 829; HRMS (ESI) m/z calcd for
＋
C H O [M+ Na] 385.1811, found 385.1814.
2
0
30 4Si
ASSOCIATED CONTENT
Supporting Information
1
13
H NMR and C NMR spectra for all the products; HPLC profiles and crystallographic data of
compound 3d (CIF). This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
Fax: 86-551-3631760. E-mail: zwang3@ustc.edu.cn
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS：
Financial support from the National Nature Science Foundation of China (21272222, 91213303,
2
1172205, J1030412) is greatly acknowledged.
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564.
(4) For examples of chiral Brønsted acid catalysts, see: Schuster, T.; Bauch, M.; Durner, G.; Gobel,
M. W. Org. Lett. 2000, 2, 179.
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Org. Lett. 2011, 13, 3868; (e) Zheng, J.; Lin, L.; Fu, K.; Zhang, Y.; Liu, X.; Feng, X. Chem. -Eur. J.
2014, 20, 14493.
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10) (a) Guo, F.; Lai, G.; Xiong, S.; Wang, S.; Wang, Z. Chem. Eur. J. 2010, 16, 6438; (b) Lai, G.;
Guo, F.; Zheng, Y.; Fang, Y.; Song, H.; Xu, K.; Wang, S.; Zha, Z.; Wang, Z. Chem. Eur. J. 2011,
7, 1114; (c) Zhang, S.; Xu, K.; Guo, F.; Hu, Y.; Zha, Z.; Wang, Z. Chem. Eur. J. 2014, 20, 979; (d)
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Li, C.; Guo, F.; Xu, K.; Zhang, S.; Hu, Y.; Zha, Z.; Wang, Z. Org. Lett. 2014, 16, 3192.
(11) Details of the crystal structure analysis are provided as Supporting Information.
CCDC-1437133 contains the supplementary crystallo-graphic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif
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1
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