A highly nucleophilic multifunctional chiral phosphane-catalyzed asymmetric intramolecular rauhut-currier reaction

Article abstract of DOI:10.1002/ejoc.201200940

An asymmetric variant of the intramolecular Rauhut-Currier (RC) reaction can be achieved using a highly nucleophilic multifunctional chiral phosphane; the corresponding cyclopentene and cyclohexene derivatives are produced in moderate to good yields and w

Full text of DOI:10.1002/ejoc.201200940

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DOI: 10.1002/ejoc.201200940
A Highly Nucleophilic Multifunctional Chiral Phosphane-Catalyzed
Asymmetric Intramolecular Rauhut–Currier Reaction
Xiao-Nan Zhang[a] and Min Shi*[a,b]
Keywords: Multifunctional chiral phosphanes / Rauhut-Currier reaction / Cyclopentene derivatives / Cyclohexene
derivatives / Organocatalysis / Cyclization / Asymmetric synthesis
An asymmetric variant of the intramolecular Rauhut–Currier
(RC) reaction can be achieved using a highly nucleophilic
multifunctional chiral phosphane; the corresponding cyclo-
pentene and cyclohexene derivatives are produced in mod-
erate to good yields and with good to excellent enantio-
selectivities.
Introduction
The Rauhut–Currier (RC) reaction, also known as the
vinylogous Morita–Baylis–Hillman (MBH) reaction, in-
volves the coupling of one active alkene/latent enolate to a
second Michael acceptor, producing a new C–C bond be-
tween the α-position of one activated alkene and the β-posi-
tion of a second alkene; a nucleophilic catalyst is central to
the reaction.[1] Since the first report by Rauhut and Currier
in 1963 of the dimerization of electron-deficient alkenes cat-
alyzed by a tertiary phosphane,[1a] the development of
asymmetric intermolecular/intramolecular RC reactions has
seen significant progress.[2,3] In particular, the asymmetric
variant of the intramolecular RC reaction to afford corre-
sponding carbocyclic derivatives with good ee values has
been achieved in recent years.[4] During our ongoing investi-
gations into the utilization of chiral multifunctional phos-
phanes in asymmetric MBH and related reactions, we real-
ized that, in the case of a Michael acceptor bearing a sub-
stituent at the β-position, a highly nucleophilic phosphane
is required to initiate the reaction due to steric issues [Equa-
tion (1)].[5,6] In this paper, we report the application of a
highly nucleophilic multifunctional chiral phosphane CP1
in the asymmetric intramolecular RC reaction, giving the
corresponding cyclohexene and cyclopentene products in
moderate to good yields and with good to high ee values
under mild conditions.
Results and Discussion
We initiated our investigations by seeking a suitable chi-
ral phosphane and the best conditions for the intramolecu-
lar RC reaction of bis(enone) 1a. After screening of the cat-
alysts, investigating the solvent effects and reaction tem-
perature on the reaction outcomes, we found that toluene
is a suitable solvent in this reaction, and the optimized reac-
tion conditions involve performing the reaction in toluene/
tert-amyl-OH (20:1) using CP1 (20 mol-%) as the catalyst
at room temperature (25 °C) for 48 h. Carried out under
these conditions, the reaction affords desired product 2a in
97% yield with 91% ee (Table 1, Entry 9) (see also Table SI-
1 and reaction procedures in the Supporting Information
for more details). Catalyst CP2 was not as effective as CP1
in this asymmetric reaction, and a less nucleophilic chiral
phosphane CP3, developed by Sasai,[6d] had no catalytic
activity in this reaction (Table 1, Entries 10 and 11). The
dimethylated chiral phosphane CP4 lacked the catalytic ac-
tivity displayed by CP1, suggesting that the phenol groups
are essential in this asymmetric RC reaction to achieve high
ee value and good yield (Table 1, Entry 12).
Under the optimal reaction conditions, we next set out
to examine the scope and limitations of this reaction using
various bis(enone)s 1; the results are summarized in Table 2.
As can be seen from Table 2, all reactions proceeded
smoothly to give the corresponding RC products 2 in mod-
erate to good yields (76–97%) with good to high ee values
(61–96%) as the (R) configuration[4b,4c] at 25 °C or 15 °C
[a] Laboratory for Advanced Materials & Institute of Fine
Chemicals, School of Chemistry & Molecular Engineering, East
China University of Science and Technology,
130 Meilong Road, Shanghai 200237, P. R. China
[b] State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, P. R. China
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200940.
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X.-N. Zhang, M. Shi
FULL PAPER
or at –30 °C for 7 d when R1 and R2 are aromatic or het-
eroaromatic groups (Table 2, Entries 1–14). Using bis-
(enone)s 1i–1k as substrates, in which the aromatic groups
bare electron-donating substituents, 40 mol-% of CP1 is re-
quired to give desired products in good yields (Table 2, En-
tries 9–11). In the case of unsymmetric bis(enone) 1o, com-
pound 2o was formed as a single product in 74% yield and
with 93% ee; isomeric material 2oЈ (R1 = 4-NO2C6H4 and
R2 = 4-MeOC6H4) was not detected (Table 2, Entry 15). By
contrast, in the case of 1p, in which R1 = C6H5 and R2 =
Me, two regioisomers 2p and 2pЈ were formed in good yield
along with similar ee values upon heating (Table 2, En-
try 16). As for aliphatic substrate 1q, the desired product 2q
was obtained in 62% yield with 64% ee when the reaction
was carried out at 80 °C (Table 2, Entry 17). Using diethyl
(2E,7E)-nona-2,7-dienedioate (1r) as substrate, no reaction
occurred, even when heated to 110 °C (Table 2, Entry 18).
Bis(enone)s 3 are difficult substrates for asymmetric RC
reactions, and ee values for such reactions have never ex-
ceeded 60% ee.[1b] Using bis(enone) 3a as substrate, reac-
tions were found to not be as effective as those involving
bis(enone)s 1 in the presence of CP1 in various solvents
under the standard conditions (Table 3, Entries 1–5). Upon
optimizing the reaction conditions, we found that lowering
the reaction temperature significantly improved the ee value
of 4a in tetrahydrofuran (THF) along with a decrease in
yield of 4a, giving the corresponding product 4a in 44%
yield with 82% ee and 38% yield and 94% ee at 0 °C or
–15 °C, respectively, in the presence of 35 mol-% of CP1
Table 1. Selected examples on the optimization of the reaction con-
ditions.[a]
Entry
Solvent
CP Time Yield
ee
[d]
[%][b] [%][c]
1
2
3
4
5
6
7
8
9
THF
Et2O
CH2Cl2
tBuOH
tBuOMe
CP1
CP1
CP1
CP1
CP1
CP1
CP1
CP1
48
48
48
48
48
48
48
48
48
48
48
48
94
94
78
97
98
74
52
97
97
45
n.r.
65
80
76
88
69
82
91
90
88
91
3
toluene
ortho-xylene
toluene/tBuOH (20:1)
toluene/tert-amyl-OH (20:1) CP1
10
11
12
toluene
toluene
toluene
CP2
CP3
CP4
–
2
[a] Reactions were performed with 1a (0.10 mmol) in the presence
of 20 mol-% of CP in solvent (1 mL) at room temp. (25 °C). [b] Iso-
lated yields. [c] Determined by chiral HPLC analysis.
Table 2. Substrate scope of asymmetric intramolecular RC reaction.[a]
Entry
Substrate
R1
R2
Time [d]
Product, yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
1a
1b
1c
1d
1e
1f
1g
1h
1i
1j
1k
1l
1m
1n
1o
1p
1q
1r
C6H5
4-NO2C6H4
4-FC6H4
2-ClC6H4
3-ClC6H4
4-ClC6H4
3-BrC6H4
4-BrC6H4
4-MeC6H4
3-MeOC6H4
4-MeOC6H4
naphth-1-yl
naphth-2-yl
furan-2-yl
4-MeOC6H4
C6H5
C6H5
4-NO2C6H4
4-FC6H4
2-ClC6H4
3-ClC6H4
4-ClC6H4
3-BrC6H4
4-BrC6H4
4-MeC6H4
3-MeOC6H4
4-MeOC6H4
naphth-1-yl
naphth-2-yl
furan-2-yl
4-NO2C6H4
Me
2
3
4
4
4
4
4
4
4
4
4
3
3
3
4
2
2
2
2a, 97
2b, 96
91
61
2c, 94[d]
2d, 95[d] (76[e]
2e, 92[d]
2f, 94 (92[d]
2g, 90[d]
2h, 92[d]
2i, 45 (92)[f]
2j, 82[f]
96[d]
81[d] (91)[e]
89[d]
89 (91)[d]
92[d]
91[d]
93 (93)[f]
89[f]
2k, 91[f]
2l, 93
92[f]
90
2m, 93
90
2n, 90[d]
2o, 74
90[d]
93
2p, 45[g] (2pЈ,[h] 17[g]
2q, 62[g]
)
66 (54)[g]
Me
OEt
Me
OEt
64[g]
2r, 0[i]
–
[a] Reactions performed with 1a (0.10 mmol) in the presence of 20 mol-% of CP1 and tert-amyl-OH (50 μL) in toluene (1 mL) at room
temp. [b] Isolated yields. [c] Determined by chiral HPLC analysis, and the absolute configuration of 2 has been assigned as (R) based on
optical rotation comparisons to previously reported compounds. [d] Reaction conducted at 15 °C. [e] Reaction conducted at –30 °C in
toluene (0.3 mL) for 7 d. [f] 40 mol-% of CP1 was used. [g] Reaction conducted in toluene at 80 °C. [h] Regioisomer of 2p (R1 = C6H5,
R2 = Me) and 2pЈ (R1 = Me, R2 = C6H5). [i] Reaction conducted in toluene at 111 °C.
2
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Catalyzed Asymmetric Intramolecular Rauhut–Currier Reactions
(Table 3, Entries 6 and 7). Further reducing the reaction fraction of 4a. The ORTEP drawing of 4a is shown in Fig-
temperature failed to improve these results (Table 3, En- ure 1 (see Supporting Information for details).[7]
try 8).
Table 3. Optimization of the reaction conditions.[a]
Entry Solvent Temp [°C] Time [d] Yield [%][b] ee [%][c]
1
2
3
4
5
THF
Et2O
CH2Cl2
tBuOMe
toluene
THF
25
25
25
25
25
0
2
2
2
2
2
7
7
7
72
32
56
24
28
44
38
9
60
45
27
49
47
82
94
96
Figure 1. ORTEP drawing of 4a.
Plausible transition states for the formation of (R)-2a
and (R)-4a shown in Figure 2 may be invoked to rationalize
the reaction outcomes. During formation of five- or six-
membered ring products, TS-1 is favored due to the steric
repulsions inherent to TS-2; corresponding products 2a or
4a are thus obtained in possessing the (R) configuration.
Intramolecular hydrogen bonding between the phenol
group and the enolate generated in situ are envisioned to
play a significant role in both cases.[5a,5h,6d]
6[d]
7[d]
8[d]
THF
THF
–15
–30
[a] Reactions were performed with 3a (0.10 mmol) in the presence
of 20 mol-% of CP1 in solvent (1.0 mL). [b] Isolated yields. [c] De-
termined by chiral HPLC analysis. [d] 35 mol-% of CP1 was used.
Using the optimized conditions, the substrate scope of
the reaction was subsequently examined, and the results of
these experiments are summarized in Table 4. The reactions
produced corresponding products 4b–4i in 18–53% yields
along with 54–95% ee values (Table 4, Entries 1–8). As for
bis(enone) 3b having a para-fluoro substituent on the aro-
matic ring, corresponding products 4b were formed in 18%
yield, due to the poor substrate solubility in THF at –15 °C
(Table 4, Entry 1). Carrying out the reaction at room tem-
perature (25 °C) improved the yields of 4b and 4d–4g, but
with significant decreases in ee for production of 4b and
4d–4g. The absolute configuration of product 4 has been
unambiguously assigned as (R) on the basis of X-ray dif-
Figure 2. Proposed transition state en route to five- and six-mem-
bered ring products catalyzed by CP1.
Table 4. Substrate scope of asymmetric intramolecular RC reac-
tion.[a]
This asymmetric catalytic system can also be used in the
intramolecular RC reaction of (2E,2ЈE)-3,3Ј-(1,2-phenyl-
ene)bis(1-phenylprop-2-en-1-one) (5), giving the desired
product 6a in 72% yield with 84% ee in toluene at 0 °C
along with achiral product 6b in 4% yield (Scheme 1). It
should also be noted that in protic solvents such as tert-
amyl-OH, achiral product 6b could be formed as the major
product using CP1 as the catalyst under otherwise identical
conditions.
Entry Substrate
R1
Time [d] Product, yield [%][b] ee [%][c]
1
2
3
4
5
6
7
8
3b
3c
3d
3e
3f
3g
3h
3i
4-FC6H4
2-ClC6H4
3-ClC6H4
4-ClC6H4
4-BrC6H4
4-MeC6H4
naphth-1-yl
furan-2-yl
7
7
7
7
7
7
7
7
4b, 18 (70)[d]
4c, 72
82 (3)[d]
67
4d, 33 (74)[d]
4e, 22 (68)[d]
4f, 20 (62)[d]
4g, 28 (63)[d]
4h, 53
57 (–6)[d]
62 (–6)[d]
60 (–7)[d]
95 (24)[d]
54
4i, 41
85
[a] Reactions were performed with 3 (0.10 mmol) in the presence
of 35 mol-% of CP1 in THF (1.0 mL) at –15 °C. [b] Isolated yields.
[c] Determined by chiral HPLC analysis. [d] Reactions were per-
formed in the presence of 20 mol-% of CP1 at room temp. (25 °C)
for 3 d.
Scheme 1. Intramolecular RC reaction of 5 catalyzed by CP1.
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X.-N. Zhang, M. Shi
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calcd. for C24H21OP+ [M]+ 356.1330, found 356.1324. [α]2D0
–120.6 (c = 1.0, CHCl3).
=
Conclusions
We have developed a novel and highly nucleophilic multi-
functional chiral phosphane CP1 catalyzed asymmetric in-
tramolecular RC reaction that uses mild conditions and en-
ables facile access to corresponding cyclopentene and cyclo-
hexene derivatives in moderate to good yields with good to
Compound (R)-CP4: White solid, 55.3 mg, 58% yield. M.p. 96–
98 °C. IR (KBr): ν = 3053, 2934, 2857, 2836, 1621, 1593, 1509,
˜
1
1456, 1403, 1267, 1247, 1089, 1018, 807, 745, 611 cm–1. H NMR
(400 MHz, CDCl3, TMS): δ = 1.58–2.01 (m, 8 H, 4 CH2), 3.02 (s,
1.1 H, OCH3), 3.08 (s, 1.9 H, OCH3), 3.81 (s, 3 H, OCH3), 7.13–
excellent enantioselectivities. Further studies on the mech- 7.24 (m, 2 H, ArH), 7.26 (dd, J = 3.2, 8.4 Hz, 1 H, ArH), 7.29–
7.40 (m, 4 H, ArH), 7.44–7.54 (m, 4 H, ArH), 7.84–7.90 (m, 3 H,
ArH), 7.98 (d, J = 8.8 Hz, 1 H, ArH) ppm. 31P NMR (CDCl3,
121.5 MHz, 85% H3PO4): δ = –20.19, –22.45 ppm. MS (EI) m/z
(%): 476 (0.24) [M]+, 447 (7.53), 446 (35.97), 445 (100), 444 (3.95),
429 (6.44), 230 (3.99), 215 (4.37). HRMS (EI): calcd. for
C32H29O2P+ [M]+ 476.1905, found 476.1906. [α]2D0 = +121.2 (c =
0.2, CHCl3).
anistic details of this catalytic system along with the devel-
opment of new asymmetric catalytic reactions with these
highly nucleophilic multifunctional chiral phosphanes are
currently underway in our laboratory.
Experimental Section
General Procedure A: To a solution of compound CP1 (0.02 mmol)
in toluene (1.0 mL) were added the corresponding bis(enone)
(0.1 mmol) and tert-amyl-OH (50 μL) at room temp. The reaction
mixture was stirred at room temp. (25 °C) until the reaction was
completed (monitoring by TLC). Then the solvent was removed
under reduced pressure, and the residue was purified by flash col-
umn chromatography to afford the desired cyclic product.
General Remarks: Melting points were determined with a digital
melting point apparatus, and temperatures are uncorrected. Optical
rotations were determined at 589 nm (sodium D line) by using a
Perkin–Elmer-341 MC digital polarimeter. [α]D values are given in
units of 10 deg–1 cm2 g–1. 1H NMR spectra were recorded with
Bruker AM-300 and AM-400 spectrometers for solutions in CDCl3
with tetramethylsilane (TMS) as an internal standard; coupling
constants J are given in Hz. 13C NMR spectra were recorded with
Bruker AM-300 and AM-400 spectrometers (75 or 100 MHz) with
complete proton decoupling (CDCl3: δ = 77.0 ppm). Infrared spec-
tra were recorded using a Perkin–Elmer PE-983 spectrometer with
absorptions reported in cm–1. Flash column chromatography was
performed using 300–400 mesh silica gel. For thin-layer chromatog-
raphy (TLC), silica gel plates (Huanghai GF254) were used. Chiral
HPLC was performed with a Waters 2487 series with chiral col-
umns [Chiralpak AD-H columns 4.6ϫ250 mm (Daicel Chemical
Ind., Ltd.)]. Mass spectra were recorded by EI, ESI, MALDI, and
HRMS was measured with an HP-5989 instrument. The prepara-
tions of chiral phosphanes CP1, CP2, and CP4 are reported in the
Supporting Information. Chiral CP3 was prepared according to
previous literature.[6d] Bis(enone)s 1 and 3 were also synthesized
according to previous literature (see Supporting Information).
General Procedure B: To a solution of compound CP1 (0.02 mmol)
in toluene (1.0 mL) were added the corresponding bis(enone)
(0.1 mmol) and tert-amyl-OH (50 μL) at room temp. The reaction
mixture was stirred at 15 °C until the reaction completed (monitor-
ing by TLC). Then the solvent was removed under reduced pres-
sure, and the residue was purified by flash column chromatography
to afford the desired cyclic product.
General Procedure C: To a solution of compound CP1 (0.02 mmol)
in toluene (0.3 mL) were added the corresponding bis(enone)
(0.1 mmol) and tert-amyl-OH (50 μL) at room temp. The reaction
mixture was stirred at –30 °C for 7 d. Then the solvent was removed
under reduced pressure, and the residue was purified by flash col-
umn chromatography to afford the desired cyclic product.
General Procedure D: To a solution of compound CP1 (0.04 mmol)
in toluene (1.0 mL) were added the corresponding bis(enone)
(0.1 mmol) and tert-amyl-OH (50 μL) at room temp. The reaction
Compound CP1: A white solid, 55.6 mg. 62% yield. M.p. 114–
116 °C. IR (KBr): ν = 3519, 3058, 2935, 2856, 1731, 1619, 1595, mixture was stirred at room temp. until the reaction was completed
˜
1465, 1421, 1382, 1265, 1140, 740 cm–1. 1H NMR (400 MHz, (monitoring by TLC). Then the solvent was removed under reduced
CDCl3, TMS): δ = 1.59–2.05 (m, 8 H, 4 CH2), 5.17 (s, 1 H, OH), pressure, and the residue was purified by flash column chromatog-
5.93 (s, 1 H, OH), 7.13–7.20 (m, 1 H, ArH), 7.27–7.52 (m, 10 H,
raphy to afford the desired cyclic product.
ArH), 7.83–7.94 (m,
4
H, ArH) ppm. 31P NMR (CDCl3,
General Procedure E: To a solution of compound CP1 (0.02 mmol)
in toluene (1.0 mL) was added the corresponding bis(enone)
(0.1 mmol) at room temp. The reaction mixture was stirred at 80 °C
for 2 d. Then the solvent was removed under reduced pressure, and
the residue was purified by flash column chromatography to afford
the desired cyclic product.
121.5 MHz, 85% H3PO4): δ = –21.33, –22.69 ppm. MS (EI) m/z
(%): 448 (3.09) [M]+, 433(6.77), 432 (36.29), 431 (100), 430 (11.58),
373 (3.99), 172 (3.97), 144 (5.67). HRMS (EI): calcd. for
C30H25O2P+ [M]+ 448.1592, found 448.1595. [α]2D0 = +137.0 (c =
0.25, CHCl3).
Compound CP2: A yellowish solid, 46.3 mg, 65% yield. M.p. 188–
General Procedure F: To
a
solution of compound CP1
190 °C. IR (KBr): ν = 3506, 3425, 3054, 2933, 2856, 1619, 1594,
˜
(0.035 mmol) in THF (1.0 mL) was added the corresponding bis-
(enone) (0.1 mmol) at room temp. The reaction mixture was stirred
at –15 °C for 7 d. Then the solvent was removed under reduced
pressure, and the residue was purified by flash column chromatog-
raphy to afford the desired cyclic products.
1514, 1501, 1345, 1265, 1203, 1143, 866, 812, 735, 683 cm–1. 1H
NMR (400 MHz, CDCl3, TMS): δ = 1.25–1.43 (m, 2 H, CH2),
1.64–1.88 (m, 5 H, 3 CH2), 2.00–2.08 (m, 1 H, CH2), 4.84 (s, 1 H,
OH), 6.92 (d, J = 8.4 Hz, 1 H, ArH), 7.20–7.25 (m, 2 H, ArH),
7.26–7.34 (m, 2 H, ArH), 7.36 (d, J = 8.8 Hz, 1 H, ArH), 7.48 (td,
J = 8.0, 1.2 Hz, 1 H, ArH), 7.70 (dd, J = 2.4, 8.8 Hz, 1 H, ArH),
7.87 (d, J = 8.0 Hz, 1 H, ArH),7.92 (d, J = 8.0 Hz, 1 H, ArH), 7.95
General Procedure G: To a solution of compound CP1 (0.02 mmol)
in toluene (0.5 mL) was added the compound 5 (0.1 mmol) at room
(d, J = 8.8 Hz, 1 H, ArH), 7.98 (d, J = 8.8 Hz, 1 H, ArH) ppm. temp. The reaction mixture was stirred at 0 °C for 3 d. Then the
31P NMR (CDCl3, 121.5 MHz, 85% H3PO4): δ = –21.71 ppm. MS
(EI) m/z (%): 356 (34.94) [M]+, 355 (18.83), 340 (27.25), 399 (100),
solvent was removed under reduced pressure, and the residue was
purified by flash column chromatography to afford the desired cy-
281 (14.69), 268 (29.67), 252 (17.67), 239 (20.96). HRMS (EI): clic products 6a and 6b.
4
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Catalyzed Asymmetric Intramolecular Rauhut–Currier Reactions
Compound 2a: General Procedure A; yield 29 mg, 97%; this is a
known compound.[8] 1H NMR (400 MHz, CDCl3, TMS): δ = 1.60–
1.81 (m, 4 H, CH2, CH2), 2.15–2.24 (m, 1 H, CH2), 2.31–2.37 (m,
8.02 (t, J = 1.6 Hz, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3,
TMS): δ = 17.9, 26.2, 26.5, 30.0, 42.4, 126.6, 127.3, 128.3, 129.0,
129.5, 129.9, 131.5, 132.9, 134.2, 134.9, 138.3, 140.3, 141.0, 146.2,
1 H, CH2), 2.82 (dd, J = 10.8, 14.8 Hz, 1 H, CH2), 3.42 (dd, J = 196.2, 198.0 ppm. Enantiomeric excess was determined by HPLC
3.2, 14.8 Hz, 1 H, CH2), 3.49–3.52 (m, 1 H, CH), 6.62–6.64 (m, 1 with a Chiralcel AD-H column [λ = 214 nm; eluent: hexane/2-pro-
H, =CH), 7.41–7.57 (m, 6 H, ArH), 7.67–7.69 (m, 2 H, ArH), 8.06– panol = 96:4; flow rate: 0.75 mL/min; tminor = 31.93 min, tmajor
=
8.09 (m, 2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ =
18.1, 26.1, 26.4, 30.3, 42.5, 128.1, 128.5, 128.6, 129.2, 131.6, 133.0,
136.7, 138.8, 141.5, 145.0, 198.1, 199.7 ppm. Enantiomeric excess
was determined by HPLC with a Chiralcel AD-H column [λ =
214 nm; eluent: hexane/2-propanol = 96:4; flow rate: 0.75 mL/min;
tminor = 23.40 min, tmajor = 31.89 min; ee = 91%; [α]2D0 = +25.1 (c =
0.90, CHCl3)].
36.00 min; ee = 89%; [α]2D0 = +19.5 (c = 0.90, CHCl3)].
Compound 2f: General Procedure B; yield 34 mg, 92%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.62–1.79 (m, 4 H, CH2, CH2), 2.19–2.25 (m, 1 H, CH2), 2.33–2.38
(m, 1 H, CH2), 2.81 (dd, J = 10.4, 14.8 Hz, 1 H, CH2), 3.34 (dd, J
= 3.2, 14.8 Hz, 1 H, CH2), 3.42–3.44 (m, 1 H, CH), 6.61–6.63 (m,
1 H, =CH), 7.41 (d, J = 8.4 Hz, 2 H, ArH), 7.43 (d, J = 8.4 Hz, 2
H, ArH), 7.63 (d, J = 8.4 Hz, 2 H, ArH), 8.00 (d, J = 8.4 Hz, 2 H,
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 17.9, 26.0,
Compound 2b: General Procedure A; yield 38 mg, 96%; this is a
known compound.[4b] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.70–1.78 (m, 4 H, CH2, CH2), 2.25–2.31 (m, 1 H, CH2), 2.39–2.45 26.4, 30.2, 42.3, 128.3, 128.8, 129.8, 130.6, 134.9, 136.8, 137.9,
(m, 1 H, CH2), 2.99 (dd, J = 9.6, 15.2 Hz, 1 H, CH2), 3.42 (dd, J 139.4, 141.1, 145.3, 196.6, 198.3 ppm. Enantiomeric excess was de-
= 3.6, 15.2 Hz, 1 H, CH2), 3.44–3.47 (m, 1 H, CH), 6.70 (t, J = termined by HPLC with a Chiralcel AD-H column [λ = 254 nm;
3.6 Hz, 1 HCH), 7.79 (d, J = 8.4 Hz, 2 H, ArH), 8.23 (d, J = eluent: hexane/2-propanol = 90:10; flow rate: 1.0 mL/min; tminor
8.4 Hz, 2 H, ArH), 8.28–8.34 (m, 4 H, ArH) ppm. 13C NMR 18.39 min, tmajor = 23.98 min; ee = 91%; [α]2D0 = +8.6 (c = 1.65,
=
(100 MHz, CDCl3, TMS): δ = 17.7, 26.3, 26.5, 29.8, 42.8, 123.4,
123.9, 129.4, 129.9, 140.9, 141.0, 144.2, 148.3, 149.3, 150.3, 196.0,
197.9 ppm. Enantiomeric excess was determined by HPLC with a
Chiralcel AD-H column [λ = 214 nm; eluent: hexane/2-propanol =
CHCl3)].
Compound 2g: General Procedure B; yield 42 mg, 90%; this is a
known compound.[4f] 1H NMR (300 MHz, CDCl3, TMS): δ =
1.63–1.77 (m, 4 H, CH2, CH2), 2.19–2.28 (m, 1 H, CH2), 2.34–2.44
(m, 1 H, CH2), 2.84 (dd, J = 10.5, 15.3 Hz, 1 H, CH2), 3.33 (dd, J
= 3.0, 15.3 Hz, 1 H, CH2), 3.44–3.47 (m, 1 H, CH), 6.67 (t, J =
3.6 Hz, 1 H, CH), 7.27–7.39 (m, 2 H, ArH), 7.58 (d, J = 7.2 Hz, 1
H, ArH), 7.63–7.70 (m, 2 H, ArH), 7.78 (s, 1 H, ArH), 8.02 (d, J
80:20; flow rate: 0.75 mL/min; tminor
= 86.05 min, tmajor =
92.42 min; ee = 61%; [α]2D0 = –10.0 (c = 0.65, CHCl3)].
Compound 2c: General Procedure B; yield 32 mg, 94%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.62–1.80 (m, 4 H, CH2, CH2), 2.17–2.27 (m, 1 H, CH2), 2.32–2.39 = 7.8 Hz, 1 H, ArH), 8.17 (s, 1 H, ArH) ppm. 13C NMR (100 MHz,
(m, 1 H, CH2), 2.79 (dd, J = 10.0, 14.8 Hz, 1 H, CH2), 3.35 (dd, J
= 3.6, 14.8 Hz, 1 H, CH2), 3.44–3.47 (m, 1 H, CH), 6.60–6.62 (m,
1 H, =CH), 7.10–7.16 (m, 4 H, ArH), 7.71–7.74 (m, 2 H, ArH),
CDCl3, TMS): δ = 17.9, 26.1, 26.4, 29.9, 42.3, 122.3, 122.9, 127.0,
127.7, 129.7, 130.1, 131.3, 131.9, 134.4, 135.8, 138.4, 140.5, 141.0,
146.3, 196.1, 198.0 ppm. Enantiomeric excess was determined by
8.08–8.12 (m, 2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, HPLC with a Chiralcel AD-H column [λ = 214 nm; eluent: hexane/
TMS): δ = 18.1, 26.1, 26.5, 30.5, 42.3, 115.2 (d, J = 21.7 Hz), 115.6 2-propanol = 96:4; flow rate: 0.75 mL/min; tminor = 27.63 min, tmajor
(d, J = 22.5 Hz), 131.1 (d, J = 9.5 Hz), 131.7 (d, J = 8.9 Hz), 133.1
(d, J = 3.0 Hz), 134.7 (d, J = 3.6 Hz), 141.2, 144.7, 164.9 (d, J =
251.2 Hz), 165.7 (d, J = 252.3 Hz), 196.6, 198.0 ppm. 19F NMR
(376 MHz, CDCl3, CFCl3): δ = –105.45, –107.27 ppm. Enantio-
meric excess was determined by HPLC with a Chiralcel AD-H col-
umn [λ = 214 nm; eluent: hexane/2-propanol = 96:4; flow rate:
0.75 mL/min; tminor = 49.21 min, tmajor = 66.33 min; ee = 96%;
[α]2D0 = +24.7 (c = 1.5, CHCl3)].
= 32.40 min; ee = 92%; [α]2D0 = +10.0 (c = 1.00, CHCl3)].
Compound 2h: General Procedure B; yield 43 mg, 92%; this is a
known compound.[4b] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.62–1.77 (m, 4 H, CH2, CH2), 2.18–2.25 (m, 1 H, CH2), 2.32–2.38
(m, 1 H, CH2), 2.80 (dd, J = 10.4, 14.8 Hz, 1 H, CH2), 3.33 (dd, J
= 3.2, 14.8 Hz, 1 H, CH2), 3.41–3.43 (m, 1 H, CH), 6.62 (t, J =
3.6 Hz, 1 H, CH), 7.53–7.64 (m, 6 H, ArH), 7.92 (d, J = 8.4 Hz, 2
H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 17.9, 26.1,
26.4, 30.2, 42.3, 126.5, 128.2, 129.9, 130.7, 131.3, 131.8, 135.3,
137.2, 141.0, 145.5, 196.8, 198.6 ppm. Enantiomeric excess was de-
Compound 2d: General Procedure C; yield 28 mg, 76%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.65–1.87 (m, 4 H, CH2, CH2), 2.14–2.32 (m, 2 H, CH2), 2.98 (dd, termined by HPLC with a Chiralcel AD-H column [λ = 214 nm;
J = 10.4, 16.8 Hz, 1 H, CH2), 3.38 (dd, J = 2.8, 16.8 Hz, 1 H, CH2),
3.47–3.50 (m, 1 H, CH), 6.56 (t, J = 3.6 Hz, 1 HCH), 7.23–7.25
eluent: hexane/2-propanol = 96:4; flow rate: 0.75 mL/min; tminor
=
74.87 min, tmajor = 95.27 min; ee = 91%; [α]2D0 = –10.6 (c = 1.45,
(m, 1 H, ArH), 7.27–7.29 (m, 1 H, ArH), 7.32–7.43 (m, 5 H, ArH), CHCl3)].
7.61–7.63 (m, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3,
Compound 2i: General Procedure D; yield 31 mg, 92%; this is a
TMS): δ = 17.4, 26.2, 26.4, 28.4, 46.0, 126.4, 126.9, 128.6, 129.1,
129.7, 130.4, 130.5, 130.86, 130.89, 131.5, 139.03, 139.09, 141.7,
148.9, 196.2, 202.2 ppm. Enantiomeric excess was determined by
HPLC with a Chiralcel AD-H column [λ = 214 nm; eluent: hexane/
2-propanol = 80:20; flow rate: 0.75 mL/min; tminor = 18.00 min,
tmajor = 21.57 min; ee = 91%; [α]2D0 = +5.0 (c = 1.00, CHCl3)].
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.59–1.79 (m, 4 H, CH2, CH2), 2.14–2.23 (m, 1 H, CH2), 2.29–2.36
(m, 1 H, CH2), 2.39 (s, 3 H, CH3), 2.41 (s, 3 H, CH3), 2.75 (dd, J
= 10.4, 14.4 Hz, 1 H, CH2), 3.37 (dd, J = 3.2, 14.8 Hz, 1 H, CH2),
3.46–3.49 (m, 1 H, CH), 6.58 (t, J = 3.6 Hz, 1 H, CH), 7.23–7.27
(m, 4 H, ArH), 7.61 (d, J = 8.4 Hz, 2 H, ArH), 7.96 (d, J = 8.4 Hz,
2 H) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 18.1, 21.4,
21.5, 26.0, 26.4, 30.5, 42.4, 128.5, 128.7, 129.2, 129.4, 134.2, 135.9,
Compound 2e: General Procedure B; yield 34 mg, 92%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.62–1.77 (m, 4 H, CH2, CH2), 2.19–2.28 (m, 1 H, CH2), 2.33–2.42 141.5, 142.2, 143.6, 143.7, 197.8, 199.3 ppm. Enantiomeric excess
(m, 1 H, CH2), 2.85 (dd, J = 10.4, 15.2 Hz, 1 H, CH2), 3.33 (dd, J was determined by HPLC with a Chiralcel AS-H column [λ =
= 3.2, 15.2 Hz, 1 H, CH2), 3.45–3.47 (m, 1 H, CH), 6.66 (t, J = 254 nm; eluent: hexane/2-propanol = 90:10; flow rate: 1.0 mL/min;
3.6 Hz, 1 H, =CH), 7.36–7.44 (m, 2 H, ArH), 7.48–7.55 (m, 3 H, tminor = 11.17 min, tmajor = 12.83 min; ee = 93%; [α]2D0 = +12.2 (c =
ArH), 7.63 (t, J = 1.6 Hz, 1 H, ArH), 7.95–7.98 (m, 1 H, ArH),
0.70, CHCl3)].
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O20940
/KAP1
Date: 20-09-12 15:42:54
Pages: 10
X.-N. Zhang, M. Shi
Compound 2j: General Procedure D; yield 30 mg, 82%; colorless 125.6, 126.6, 126.7, 127.7, 127.8, 127.9, 128.1, 128.35, 128.37,
FULL PAPER
oil. IR (KBr): ν = 2928, 1685, 1676, 1638, 1484, 1459, 1430, 1274,
129.2, 129.8, 130.3, 130.5, 132.3, 132.6, 134.0, 134.9, 135.5, 136.0,
˜
1
1042, 788, 754, 685 cm–1. H NMR (400 MHz, CDCl3, TMS): δ = 141.7, 144.9, 198.1, 199.7 ppm. Enantiomeric excess was deter-
1.61–1.78 (m, 4 H, CH2, CH2), 2.16–2.23 (m, 1 H, CH2), 2.31–2.37 mined by HPLC with a Chiralcel AS-H column [λ = 254 nm; elu-
(m, 1 H, CH2), 2.79 (dd, J = 10.4, 14.8 Hz, 1 H, CH2), 3.40 (dd, J
= 3.2, 14.8 Hz, 1 H, CH2), 3.49–3.51 (m, 1 H, CH), 3.84 (s, 3 H,
OCH3), 3.87 (s, 3 H, OCH3), 6.65 (t, J = 3.6 Hz, 1 H, CH), 7.04–
7.11 (m, 2 H, ArH), 7.21–7.25 (m, 2 H, ArH), 7.31–7.39 (m, 2 H,
ent: hexane/2-propanol = 90:10; flow rate: 1.0 mL/min; tminor =
15.89 min, tmajor = 24.59 min; ee = 90%; [α]2D0 = –29.4 (c = 1.90,
CHCl3)].
Compound 2n: General Procedure B; yield 26 mg, 90%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.65–1.77 (m, 4 H, CH2, CH2), 2.21–2.28 (m, 1 H, CH2), 2.33–2.40
(m, 1 H, CH2), 2.67 (dd, J = 10.8, 14.8 Hz, 1 H, CH2), 3.10 (dd, J
= 3.2, 14.8 Hz, 1 H, CH2), 3.45–3.48 (m, 1 H, CH), 6.51–6.54 (m,
2 H, ArH), 6.99–7.02 (m, 1 H, =CH), 7.11–7.12 (m, 1 H, ArH),
7.40–7.42 (m, 1 H, ArH), 7.56–7.57 (m, 1 H, ArH), 7.63–7.64 (m,
1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 17.9,
26.0, 26.3, 30.6, 42.2, 111.8, 112.1, 118.2, 119.2, 140.8, 142.1, 146.4,
146.5, 152.27, 152.31, 183.6, 188.2 ppm. Enantiomeric excess was
determined by HPLC with a Chiralcel AD-H column [λ = 214 nm;
ArH), 7.61 (s, 1 H, ArH), 7.68 (d, J = 8.0 Hz, 1 H, ArH) ppm. 13
C
NMR (100 MHz, CDCl3, TMS): δ = 18.0, 26.1, 26.4, 30.4, 42.6,
55.38, 55.44, 112.4, 114.0, 117.7, 119.7, 121.1, 121.8, 129.0, 129.6,
138.0, 140.1, 141.4, 145.0, 159.4, 159.8, 197.7, 199.4 ppm. MS (EI)
m/z (%): 364 (44.05) [M]+, 229 (48.60), 214 (17.53), 135 (100), 121
(28.41), 107 (57.55), 92 (35.59), 77 (68.86). HRMS (EI): calcd. for
C23H24O4 [M]+ 364.1675, found 364.1679. Enantiomeric excess
+
was determined by HPLC with a Chiralcel AD-H column [λ =
214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/
min; tminor = 21.98 min, tmajor = 26.49 min; ee = 89%; [α]2D0 = +17.0
(c = 0.70, CHCl3)].
eluent: hexane/2-propanol = 80:20; flow rate: 0.75 mL/min; tminor
=
22.73 min, tmajor = 32.25 min; ee = 90%; [α]2D0 = –6.9 (c = 1.10,
Compound 2k: General Procedure D; yield 33 mg, 91%; this is a
known compound.[4b] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.59–1.81 (m, 4 H, CH2, CH2), 2.14–2.22 (m, 1 H, CH2), 2.29–2.36
(m, 1 H, CH2), 2.70 (dd, J = 10.8, 14.4 Hz, 1 H, CH2), 3.33 (dd, J
= 2.8, 14.4 Hz, 1 H, CH2), 3.45–3.47 (m, 1 H, CH), 3.85 (s, 3 H,
OCH3), 3.87 (s, 3 H, OCH3), 6.52–6.54 (m, 1 H, =CH), 6.92–6.95
(m, 4 H, ArH), 7.72–7.76 (m, 2 H, ArH), 8.03–8.07 (m, 2 H,
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 18.3, 25.9,
26.6, 31.1, 42.3, 55.38, 55.40, 113.4, 113.7, 129.8, 130.8, 131.1,
131.7, 141.6, 142.3, 162.7, 163.4, 197.0, 198.3 ppm. Enantiomeric
excess was determined by HPLC with a Chiralcel AD-H column [λ
= 214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.75 mL/
min; tminor = 28.25 min, tmajor = 41.05 min; ee = 92%; [α]2D0 = –4.2
(c = 0.40, CHCl3)].
CHCl3)].
Compound 2o: General Procedure A; yield 28 mg, 74%; this is a
known compound.[4b] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.62–1.84 (m, 4 H, 2CH2, 2CH2), 2.19–2.27 (m, 1 H, CH2), 2.34–
2.43 (m, 1 H, CH2), 2.87 (dd, J = 9.6, 14.8 Hz, 1 H, CH2), 3.31
(dd, J = 3.6, 14.4 Hz, 0.5 H, CH2), 3.32 (dd, J = 3.6, 14.8 Hz, 1 H,
CH2), 3.42–3.51 (m, 1 H, CH), 3.87 (s, 3 H, CH3), 6.60–6.62 (m, 1
H, =CH), 6.95 (d, J = 8.8 Hz, 2 H, ArH), 7.81 (d, J = 8.8 Hz, 2
H, ArH), 8.05 (d, J = 8.8 Hz, 2 H, ArH), 8.29 (d, J = 8.8 Hz, 2 H,
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 17.8, 26.33,
26.40, 30.2, 41.8, 55.4, 113.7, 123.3, 129.8, 129.9, 130.6, 141.7,
144.3, 147.2, 149.2, 163.4, 195.9, 198.0 ppm. Enantiomeric excess
was determined by HPLC with a Chiralcel AD-H column [λ =
214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.75 mL/
min; tminor = 44.37 min, tmajor = 47.58 min; ee = 93%; [α]2D0 = –6.1
(c = 0.85, CHCl3)].
Compound 2l: General Procedure A; yield 37 mg, 93%; colorless
oil. IR (KBr): ν = 3060, 2929, 2864, 1679, 1644, 1508, 1282, 1245,
˜
1
1143, 803, 780, 734 cm–1. H NMR (400 MHz, CDCl3, TMS): δ =
1.64–1.90 (m, 4 H, CH2, CH2), 2.09–2.17 (m, 1 H, CH2), 2.21–2.29
(m, 1 H, CH2), 3.01 (dd, J = 10.8, 15.2 Hz, 1 H, CH2), 3.63–3.66
(m, 1 H, CH), 3.75 (dd, J = 2.8, 15.2 Hz, 1 H, CH2), 6.64 (t, J =
3.6 Hz, 1 H, =CH), 7.45–7.47 (m, 2 H, ArH), 7.48–7.62 (m, 5 H,
ArH), 7.86–7.92 (m, 3 H, ArH), 7.96–8.00 (m, 2 H, ArH), 8.18 (dd,
J = 1.2, 7.6 Hz, 1 H, ArH), 8.71 (d, J = 8.8 Hz, 1 H, ArH) ppm.
13C NMR (100 MHz, CDCl3, TMS): δ = 17.7, 26.4, 26.5, 30.0,
45.8, 124.3, 124.6, 125.4, 125.9, 126.30, 126.31, 126.39, 127.0,
127.9, 128.3, 128.4, 128.5, 130.3, 130.4, 130.9, 132.6, 133.6, 134.0,
135.3, 137.3, 143.3, 148.3, 199.3, 204.0 ppm. MS (EI) m/z (%): 404
(29.45) [M]+, 250 (12.91), 249 (62.72), 234 (19.95), 155 (68.04), 128
Compound 2p: General Procedure E; yield 15 mg, 62%; this is a
known compound (a mixture of 2p and 2pЈ).[9] 1H NMR
(400 MHz, CDCl3, TMS): δ = 1.45–1.81 (m, 5.7 H, 2 CH2, 2 CH2),
2.11–2.37 (m, 7.7 H, CH2, CH3, CH2, CH3), 2.46 (dd, J = 10.0,
16.0 Hz, 1 H, CH2), 2.65–2.72 (m, 1.5 H, CH2, CH2), 3.33–3.38
(m, 1.8 H, CH, CH, CH2), 6.56 (t, J = 4.0 Hz, 1 H, =CH), 7.01 (t,
J = 4.0, Hz, 0.4 H, =CH), 7.39–7.50 (m, 4.2 H, ArH, ArH), 7.64–
7.66 (m, 2 H, ArH), 8.10–8.13 (m, 0.8 H, ArH) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 16.7, 18.1, 25.52, 25.54, 25.9, 26.1,
26.9, 28.7, 29.1, 29.8, 42.5, 47.3, 128.0, 128.40, 128.44, 129.1, 131.5,
132.8, 136.6, 138.5, 141.2, 142.2, 143.0, 144.3, 197.8, 199.0, 199.8,
208.0 ppm. Enantiomeric excess of 2p was determined by HPLC
with a Chiralcel AD-H column [λ = 214 nm; eluent: hexane/2-pro-
+
(15.55), 127 (100), 126 (13.38). HRMS (EI): calcd. for C29H24O2
[M]+ 404.1776, found 404.1773. Enantiomeric excess was deter-
mined by HPLC with a Chiralcel AS-H column [λ = 254 nm; elu-
panol = 96:4; flow rate: 0.75 mL/min; tminor = 25.32 min, tmajor
=
ent: hexane/2-propanol = 96:4; flow rate: 0.75 mL/min; tminor
=
28.40 min; ee = 54%]; enantiomeric excess of 2pЈ was determined
by HPLC with a Chiralcel AD-H column [λ = 214 nm; eluent: hex-
ane/2-propanol = 96:4; flow rate: 0.75 mL/min; tminor = 23.54 min,
tmajor = 41.23 min; ee = 66%; [α]2D0 = –5.5 (c = 1.25, CHCl3)] (a
mixture of 2p and 2pЈ).
47.76 min, tmajor = 51.40 min; ee = 90%; [α]2D0 = +63.0 (c = 1.85,
CHCl3)].
Compound 2m: General Procedure A; yield 37 mg, 93%; this is a
known compound.[4f] 1H NMR (400 MHz, CDCl3, TMS): δ =
1.64–1.82 (m, 4 H, CH2, CH2), 2.16–2.25 (m, 1 H, CH2), 2.33–2.41 Compound 2q: General Procedure E; yield 11 mg, 62%; this is a
(m, 1 H, CH2), 2.98 (dd, J = 10.4, 14.4 Hz, 1 H, CH2), 3.60 (dd, J
known compound.[4b] 1H NMR (400 MHz, CDCl3, TMS): δ =
= 3.2, 14.4 Hz, 1 H, CH2), 3.62–3.66 (m, 1 H, CH), 6.70 (t, J = 1.50–1.68 (m, 4 H, 2CH2), 2.17 (s, 3 H, CH3), 2.19–2.33 (m, 6 H,
3.6, Hz, 1 H, =CH), 7.48–7.59 (m, 4 H, ArH), 7.81–7.95 (m, 6 H,
CH2, CH3, CH2), 2.60 (dd, J = 2.8, 15.6 Hz, 1 H, CH2), 3.16–3.19
ArH), 8.00 (d, J = 7.6 Hz, 1 H, ArH), 8.10 (dd, J = 1.6, 8.4 Hz, 1
(m, 1 H, CH), 6.96 (t, J = 4.0, Hz, 1 H, =CH) ppm. 13C NMR
H, ArH), 8.19 (s, 1 H, ArH), 8.68 (s, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 16.9, 25.5, 26.0, 26.1, 27.6, 29.6,
(100 MHz, CDCl3, TMS): δ = 18.2, 26.2, 26.6, 30.8, 42.7, 124.1,
47.5, 142.0, 142.5, 198.7, 208.2 ppm. Enantiomeric excess was de-
6
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20940
/KAP1
Date: 20-09-12 15:42:54
Pages: 10
Catalyzed Asymmetric Intramolecular Rauhut–Currier Reactions
termined by HPLC with a Chiralcel AD-H column [λ = 214 nm;
41.3, 42.2, 126.4, 126.9, 128.3, 128.8, 129.6, 129.9, 131.9, 132.9,
134.4, 134.9, 138.4, 140.4, 145.6, 148.9, 192.5, 198.2 ppm. MS
(ESI): m/z (%) = 359.2 (100) [M + H]+. HRMS (ESI): calcd. for
eluent: hexane/2-propanol = 96:4; flow rate: 0.60 mL/min; tminor
=
25.17 min, tmajor = 26.91 min; ee = 64%; [α]2D0 = –6.9 (c = 0.55,
+
CHCl3)].
C20H17Cl2O2 [M + H]+ 359.06001, found 359.0594. Enantiomeric
excess was determined by HPLC with a Chiralcel AD-H column [λ
= 214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/
min; tminor = 8.90 min, tmajor = 9.97 min; ee = 57%; [α]2D0 = +39.0
(c = 0.70, CHCl3)].
Compound 4a: General Procedure F; colorless oil, yield 11 mg,
38%; this is a known compound.[4a] 1H NMR (400 MHz, CDCl3,
TMS): δ = 1.73–1.82 (m, 1 H, CH2), 2.27–2.36 (m, 1 H, CH2),
2.47–2.57 (m, 1 H, CH2), 2.62–2.72 (m, 1 H, CH2), 2.82 (dd, J =
11.2, 16.4 Hz, 1 H, CH2), 3.70–3.78 (m, 2 H, CH, CH2), 6.56–6.57
(m, 1 H, =CH), 7.41–7.46 (m, 4 H, ArH), 7.50–7.55 (m, 2 H, ArH),
7.74–7.77 (m, 2 H, ArH), 8.03–8.05 (m, 2 H, ArH) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 29.5, 32.6, 41.6, 42.4, 128.2, 128.3,
Compound 4e: General Procedure F; colorless oil, yield 8 mg, 22%.
IR (KBr): ν = 3078, 2927, 1684, 1641, 1586, 1569, 1486, 1400, 1281,
˜
1174, 1091, 1013, 991, 833, 753 cm–1. 1H NMR (400 MHz, CDCl3,
TMS): δ = 1.72–1.81 (m, 1 H, CH2), 2.27–2.36 (m, 1 H, CH2),
128.6, 128.9, 132.0, 132.9, 136.9, 139.0, 146.1, 147.9, 194.2, 2.50–2.60 (m, 1 H, CH2), 2.64–2.74 (m, 1 H, CH2), 2.80 (dd, J =
199.7 ppm. Enantiomeric excess was determined by HPLC with a
Chiralcel AD-H column [λ = 214 nm; eluent: hexane/2-propanol =
80:20; flow rate: 0.70 mL/min; tminor = 9.37 min, tmajor = 12.03 min;
ee = 94%; [α]2D0 = +108.1 (c = 0.60, CHCl3)].
10.8, 16.4 Hz, 1 H, CH2), 3.67–3.72 (m, 2 H, CH+CH2), 6.57–6.58
(m, 1 H, =CH), 7.41–7.44 (m, 4 H, ArH), 7.69–7.72 (m, 2 H, ArH),
7.96–7.98 (m, 2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3,
TMS): δ = 29.4, 32.6, 41.5, 42.1, 128.5, 128.8, 129.7, 130.2, 135.1,
137.1, 138.4, 139.4, 145.7, 148.1, 192.8, 198.3 ppm. MS (ESI): m/z
Compound 4b: General Procedure F; a yellowish solid, yield 6 mg,
(%) = 359.2 (100) [M + H]+. HRMS (ESI): calcd. for C20H17Cl2O2
+
18%. M.p. 87–88 °C. IR (KBr): ν = 3076, 2936, 1683, 1639, 1597,
˜
[M + H]+ 359.06001, found 359.0604. Enantiomeric excess was de-
termined by HPLC with a Chiralcel AD-H column [λ = 214 nm;
1505, 1408, 1359, 1228, 1156, 1097, 993, 836, 757, 614, 594 cm–1.
1H NMR (400 MHz, CDCl3, TMS): δ = 1.73–1.82 (m, 1 H, CH2),
2.26–2.36 (m, 1 H, CH2), 2.50–2.58 (m, 1 H, CH2), 2.64–2.73 (m,
1 H, CH2), 2.77–2.84 (m, 1 H, CH2), 3.68–3.73 (m, 2 H, CH, CH2),
6.56–6.57 (m, 1 H, =CH), 7.08–7.14 (m, 4 H, ArH), 7.78–7.82 (m,
eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/min; tminor
=
13.17 min, tmajor = 18.27 min; ee = 62%; [α]2D0 = +34.0 (c = 0.50,
CHCl3)].
2 H, ArH), 8.04–8.08 (m, 2 H, ArH) ppm. 13C NMR (100 MHz, Compound 4f: General Procedure F; white solid, yield 9 mg, 20%.
CDCl3, TMS): δ = 29.5, 32.6, 41.7, 42.1, 115.3 (d, J = 20.5 Hz), M.p. 74–76 °C. IR (KBr): ν = 3065, 2926, 1685, 1637, 1584, 1566,
115.5 (d, J = 21.9 Hz), 130.9 (d, J = 9.0 Hz), 131.4 (d, J = 8.8 Hz), 1481, 1395, 1283, 1175, 1070, 1010, 990, 828, 748 cm–1. H NMR
˜
1
133.3 (d, J = 3.0 Hz), 135.1 (d, J = 3.0 Hz), 145.9, 147.6, 165.1 (d,
J = 251.8 Hz), 165.6 (d, J = 254.3 Hz), 192.5, 197.9 ppm. 19F NMR
(376 MHz, CDCl3, CFCl3): δ = –110.32, –111.50 ppm. MS (ESI):
m/z (%) = 327.3 (100) [M + H]+. HRMS (ESI): calcd. for
(300 MHz, CDCl3, TMS): δ = 1.70–1.81 (m, 1 H, CH2), 2.25–2.38
(m, 1 H, CH2), 2.48–2.61 (m, 1 H, CH2), 2.62–2.72 (m, 1 H, CH2),
2.80 (dd, J = 10.5, 15.9 Hz, 1 H, CH2), 3.66–3.72 (m, 2 H,
CH+CH2), 6.57–6.59 (m, 1 H, =CH), 7.57–7.64 (m, 6 H, ArH),
7.90 (d, J = 8.4 Hz, 2 H, ArH) ppm. 13C NMR (75 MHz, CDCl3,
TMS): δ = 29.4, 32.6, 41.4, 42.1, 127.0, 128.1, 129.8, 130.4, 131.5,
131.8, 135.4, 137.5, 145.7, 148.3, 192.9, 198.5 ppm. MS (ESI): m/z
+
C20H17F2O2 [M + H]+ 327.1191, found 327.1196. Enantiomeric
excess was determined by HPLC with a Chiralcel AD-H column [λ
= 214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/
min; tminor = 10.48 min, tmajor = 13.75 min; ee = 82%; [α]2D0 = +51.0
(c 0.50, CHCl3)].
+
(%) = 449.2 (100) [M + H]+. HRMS (ESI): calcd. for C20H17Br2O2
[M + H]+ 446.95898, found 446.9600. Enantiomeric excess was de-
termined by HPLC with a Chiralcel AD-H column [λ = 214 nm;
Compound 4c: General Procedure F; a yellowish oil, yield 26 mg,
eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/min; tminor
=
72%. IR (KBr): ν = 3062, 2922, 2851, 1697, 1650, 1608, 1590, 1469,
˜
15.82 min, tmajor = 22.32 min; ee = 60%; [α]2D0 = +38.0 (c = 0.45,
1432, 1360, 1287, 1057, 758 cm–1. 1H NMR (400 MHz, CDCl3,
TMS): δ = 1.79–1.87 (m, 1 H, CH2), 2.35–2.44 (m, 1 H, CH2),
2.46–2.56 (m, 1 H, CH2), 2.59–2.69 (m, 1 H, CH2), 3.01 (dd, J =
10.4, 17.6 Hz, 1 H, CH2), 3.67–3.72 (m, 2 H, CH+CH2), 6.41–
6.43 (m, 1 H, =CH), 7.29–7.43 (m, 6 H, ArH), 7.54–7.56 (m, 2 H,
CHCl3)].
Compound 4g: General Procedure F; white solid, yield 9 mg, 28%.
M.p. 86–88 °C. IR (KBr): ν = 3070, 2922, 1680, 1637, 1605, 1569,
˜
1455, 1406, 1356, 1283, 1198, 1179, 1115, 979, 813, 745 cm–1. 1H
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 30.0, 32.5, NMR (400 MHz, CDCl3, TMS): δ = 1.72–1.80 (m, 1 H, CH2),
39.8, 46.4, 126.4, 126.9, 128.5, 128.9, 130.0, 130.5, 130.66, 130.75,
130.83, 131.5, 139.41, 139.42, 146.9, 151.4, 193.0, 202.5 ppm. MS
(ESI): m/z (%) = 359.2 (100) [M + H]+. HRMS (ESI): calcd. for
2.24–2.35 (m, 1 H, CH2), 2.40 (s, 3 H, CH3), 2.42 (s, 3 H, CH3),
2.48–2.58 (m, 1 H, CH2), 2.62–2.71 (m, 1 H, CH2), 2.75 (dd, J =
10.8, 16.4 Hz, 1 H, CH2), 3.66–3.76 (m, 2 H, CH2+CH), 6.54–6.56
(m, 1 H, =CH), 7.24–7.26 (m, 4 H, ArH), 7.68 (d, J = 8.0 Hz, 2
H, ArH), 7.94 (d, J = 8.0 Hz, 2 H, ArH) ppm. 13C NMR
(100 MHz, CDCl3, TMS): δ = 21.56, 21.61, 29.5, 32.6, 41.8, 42.4,
128.4, 128.9, 129.1, 129.2, 134.4, 136.3, 142.7, 143.7, 146.2, 147.0,
194.0, 199.5 ppm. MS (EI): m/z (%) = 318 (16.71) [M]+, 199 (24.22),
185(6.42), 184 (18.17), 120 (9.27), 119 (100), 91 (51.8), 65 (13.67).
C20H17Cl2O2 [M + H]+ 359.06001, found 359.0610. Enantiomeric
+
excess was determined by HPLC with a Chiralcel AD-H column [λ
= 214 nm; eluent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/
min; tminor = 10.91 min, tmajor = 11.97 min; ee = 67%; [α]2D0 = +45.0
(c = 1.0, CHCl3)].
Compound 4d: General Procedure F; colorless oil, yield 12 mg,
HRMS (EI): calcd. for C22H22O2 [M]+ 318.1620, found 318.1618.
+
33%. IR (KBr): ν = 3067, 2932, 1688, 1642, 1605, 1567, 1420, 1356,
˜
Enantiomeric excess was determined by HPLC with a Chiralcel
AD-H column [λ = 214 nm; eluent: hexane/2-propanol = 80:20;
flow rate: 0.70 mL/min; tminor = 17.52 min, tmajor = 27.07 min; ee =
95%; [α]2D0 = +90.0 (c = 0.40, CHCl3)].
1285, 1257, 1198, 1077, 789, 738, 723, 681 cm–1. 1H NMR
(400 MHz, CDCl3, TMS): δ = 1.72–1.80 (m, 1 H, CH2), 2.30–2.39
(m, 1 H, CH2), 2.52–2.61 (m, 1 H, CH2), 2.65–2.75 (m, 1 H, CH2),
2.85 (dd, J = 10.4, 16.0 Hz, 1 H, CH2), 3.66–3.73 (m, 2 H, CH +
CH2), 6.61–6.62 (m, 1 H, =CH), 7.37–7.43 (m, 2 H, ArH), 7.50– Compound 4h: General Procedure F; yellowish oil, yield 21 mg,
7.53 (m, 2 H, ArH), 7.61–7.64 (m, 1 H, ArH), 7.70–7.71 (m,1 H,
53%. IR (KBr): ν = 3131, 2941, 1671, 1630, 1564, 1467, 1392, 1299,
˜
ArH), 7.90–7.93 (m, 1 H, ArH), 7.98 (t, J = 2.0 Hz, 1 H,
1166, 1083, 1013, 883, 796, 761, 595 cm–1. 1H NMR (400 MHz,
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 29.5, 32.7, CDCl3, TMS): δ = 1.88–1.96 (m, 1 H, CH2), 2.33–2.51 (m, 2 H,
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O20940
/KAP1
Date: 20-09-12 15:42:54
Pages: 10
X.-N. Zhang, M. Shi
FULL PAPER
CH2 + CH2), 2.58–2.67 (m, 1 H, CH2), 3.07 (dd, J = 10.8, 16.0 Hz,
1 H, CH2), 3.85–3.87 (m, 1 H, CH), 3.99 (dd, J = 2.8, 16.0 Hz, 1
China (973)-2010CB833302, the Fundamental Research Funds for
the Central Universities and the National Natural Science Founda-
H, CH2), 6.44–6.45 (m, 1 H, =CH), 7.42–7.61 (m, 7 H, ArH), 7.86 tion of China for financial support (20928001, 21072206, 20472096,
(d, J = 7.6 Hz, 2 H, ArH), 7.91 (d, J = 8.4 Hz, 1 H, ArH), 7.96
(dd, J = 8.4 Hz, 1 H, ArH), 8.03–8.12 (m, 2 H, ArH), 8.68 (d, J =
9.2 Hz, 1 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ =
29.8, 32.6, 41.2, 45.8, 124.3, 124.6, 125.4, 125.9, 126.37, 126.40,
126.9, 127.1, 127.9, 128.1, 128.4, 128.5, 130.3, 130.5, 130.8, 132.6,
133.7, 134.1, 135.8, 137.3, 148.3, 150.6, 195.8, 204.1 ppm. MS
(ESI): m/z (%) = 391.4 (100) [M + H]+. HRMS (ESI): calcd. for
C28H23O2+ [M + H]+ 391.16926, found 391.1683. Enantiomeric ex-
cess was determined by HPLC with a Chiralcel AD-H column [λ
= 214 nm; eluent: hexane/2-propanol = 96:4; flow rate: 0.75 mL/
min; tminor = 33.82 min, tmajor = 40.58 min; ee = 54%; [α]2D0 = +59.0
(c = 0.85, CHCl3)].
20872162, 20672127, 21121062 and 20732008).
[1] a) M. M. Rauhut, H. Currier, US Patent 307,499,919,630,122,
American Cyanamid Co., 1963; Chem. Abstr. 1963, 58, 11224a;
b) for a review, see: C. E. Aroyan, A. Dermenci, S. J. Miller,
Tetrahedron 2009, 65, 4069–4084.
[2] For reviews, see: a) D. Basavaiah, A. J. Rao, T. Satyanarayana,
Chem. Rev. 2003, 103, 811–892; b) D. Basavaiah, B. S. Reddy,
S. S. Badsara, Chem. Rev. 2010, 110, 5447–5674.
[3] a) J. Wang, H. Xie, L. Zu, W. Wang, Angew. Chem. 2008, 120,
4245–4247; Angew. Chem. Int. Ed. 2008, 47, 4177–4179; b) T.
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S. J. Miller, J. Am. Chem. Soc. 2007, 129, 256–257; c) C. E.
Aroyan, A. Dermenci, S. J. Miller, J. Org. Chem. 2010, 75,
5784–5796; d) F. Seidel, J. A. Gladysz, Synlett 2007, 986–988;
e) E. M. López, R. P. Herrera, T. Marks, W. C. Jacobs, D.
Könning, R. M. de Figueiredo, M. Christmann, Org. Lett.
2009, 11, 4116–4119; f) J.-J. Gong, T.-Z. Li, K. Pana, X.-Y.
Wu, Chem. Commun. 2011, 47, 1491–1493; g) P. S. Selig, S. J.
Miller, Tetrahedron Lett. 2011, 52, 2148–2151; h) S. Takizawa,
T. M.-N. Nguyen, A. Grossmann, D. Enders, H. Sasai, Angew.
Chem. 2012, 124, 5519–5522; Angew. Chem. Int. Ed. 2012, 51,
5423–5426.
Compound 4i: General Procedure F; yield 11 mg, 41%; this is a
known compound.[4a] IR (KBr): ν = 3056, 2926, 1681, 1643, 1592,
˜
1
1574, 1507, 1435, 1351, 1278, 1101, 947, 781, 737 cm–1. H NMR
(400 MHz, CDCl3, TMS): δ = 1.75–1.83 (m, 1 H, CH2), 2.20–2.29
(m, 1 H, CH2), 2.53–2.62 (m, 1 H, CH2), 2.65–2.75 (m, 2 H,
CH2+CH2), 3.47 (dd, J = 3.2, 15.2 Hz, 1 H, CH2), 3.65–3.75 (m, 1
H, CH), 6.52 (dd, J = 1.6, 3.6 Hz, 1 H, ArH), 6.55 (dd, J = 1.6,
3.6 Hz, 1 H, ArH), 7.10–7.11 (m, 1 H, =CH), 7.20 (dd, J = 0.8,
3.6 Hz, 1 H, ArH), 7.33 (dd, J = 0.8, 3.6 Hz, 1 H, ArH), 7.57 (dd,
J = 0.8, 3.6 Hz, 1 H, ArH), 7.62 (dd, J = 0.8, 1.6 Hz, 1 H,
ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ = 28.7, 32.8,
41.8, 42.2, 112.0, 112.1, 117.8, 118.2, 145.0, 146.2, 146.40, 146.42,
152.5, 153.0, 179.4, 188.6 ppm. Enantiomeric excess was deter-
mined by HPLC with a Chiralcel AD-H column [λ = 214 nm; elu-
ent: hexane/2-propanol = 80:20; flow rate: 0.70 mL/min; tminor
=
[5] a) M. Shi, L.-H. Chen, C.-Q. Li, J. Am. Chem. Soc. 2005, 127,
3790–3800; b) M. Shi, C.-Q. Li, Tetrahedron: Asymmetry 2005,
16, 1385–1391. For reviews, see: c) X. Lu, C. Zhang, Z. Xu,
Acc. Chem. Res. 2001, 34, 535–544; d) J. L. Methot, W. R.
Roush, Adv. Synth. Catal. 2004, 346, 1035–1050; e) L.-W. Ye,
J. Zhou, Y. Tang, Chem. Soc. Rev. 2008, 37, 1140–1152; f) B. J.
Cowen, S. J. Miller, Chem. Soc. Rev. 2009, 38, 3102–3116; g)
A. Marinetti, A. Voituriez, Synlett 2010, 174–194; h) Y. Wei,
M. Shi, Acc. Chem. Res. 2010, 43, 1005–1018.
11.55 min, tmajor = 14.92 min; ee = 85%; [α]2D0 = +28.0 (c = 0.5,
CHCl3)].
Compound 6a: General Procedure G; yield 24 mg, 72%; this is a
known compound.[9] 1H NMR (400 MHz, CDCl3, TMS): δ = 3.18
(dd, J = 9.6, 16.8 Hz, 1 H, CH2), 4.05 (dd, J = 2.8, 16.8 Hz, 1 H,
CH2), 4.67–4.69 (m, 1 H, CH), 7.30–7.36 (m, 2 H, =CH+ArH),
7.43–7.60 (m, 9 H, ArH), 7.83 (d, J = 8.0 Hz, 2 H, ArH), 8.02 (d,
J = 8.0 Hz, 2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS):
δ = 39.4, 45.2, 124.0, 124.4, 127.3, 128.1, 128.2, 128.5, 128.8, 131.8,
133.0, 136.7, 139.1, 141.5, 144.1, 147.3, 149.3, 192.8, 198.3 ppm.
Enantiomeric excess was determined by HPLC with a Chiralcel
AD-H column [λ = 214 nm; eluent: hexane/2-propanol = 70:30;
flow rate: 0.80 mL/min; tminor = 19.31 min, tmajor = 23.63 min; ee =
84%; [α]2D0 = –240.8 (c = 0.8, CHCl3)].
[6] For selected papers on chiral phosphanes for asymmetric catal-
ysis, see: a) G. Zhu, Z. Chen, Q. Jiang, D. Xiao, P. Cao, X.
Zhang, J. Am. Chem. Soc. 1997, 119, 3836–3837; b) J. E. Wil-
son, G. C. Fu, Angew. Chem. 2006, 118, 1454–1457; Angew.
Chem. Int. Ed. 2006, 45, 1426–1429; c) D. J. Wallace, R. L.
Sidda, R. A. Reamer, J. Org. Chem. 2007, 72, 1051–1054; d) K.
Matsui, S. Takizawa, H. Sasai, Synlett 2006, 5, 761–763; e) T.
Kano, Y. Yamaguchi, O. Tokuda, K. Maruoka, J. Am. Chem.
Soc. 2005, 127, 16408–16409; f) Y.-Q. Fang, E. N. Jacobsen, J.
Am. Chem. Soc. 2008, 130, 5660–5661; g) M.-J. Qi, T. Ai, M.
Shi, G. Li, Tetrahedron 2008, 64, 1181–1186; h) Y.-K. Chung,
G. C. Fu, Angew. Chem. 2009, 121, 2259–2261; Angew. Chem.
Int. Ed. 2009, 48, 2225–2228; i) H. Xiao, Z. Chai, C.-W. Zheng,
Y.-Q. Yang, W. Liu, J.-K. Zhang, G. Zhao, Angew. Chem. 2010,
122, 4569–4572; Angew. Chem. Int. Ed. 2010, 49, 4467–4470; j)
X. Han, Y. Wang, F. Zhong, Y. Lu, J. Am. Chem. Soc. 2011,
133, 1726–1729; k) N. Pinto, P. Retailleau, A. Voituriez, A.
Marinetti, Chem. Commun. 2011, 47, 1015–1017; l) J.-W. Sun,
G. C. Fu, J. Am. Chem. Soc. 2010, 132, 4568–4569; m) Y. Fuji-
wara, G. C. Fu, J. Am. Chem. Soc. 2011, 133, 12293–12297; n)
F.-R. Zhong, Y.-Q. Wang, X.-Y. Han, K.-W. Huang, Y.-X. Lu,
Org. Lett. 2011, 13, 1310–1313; o) F.-R. Zhong, X.-Y. Han, Y.-
Q. Wang, Y.-X. Lu, Angew. Chem. 2011, 123, 7983–7987; An-
gew. Chem. Int. Ed. 2011, 50, 7837–7841; p) A. Voituriez, A.
Panossian, N. Fleury-Brégeot, P. Retailleau, A. Marinetti, J.
Am. Chem. Soc. 2008, 130, 14030–14031; q) B. J. Cowen, L. B.
Saunders, S. J. Miller, J. Am. Chem. Soc. 2009, 131, 6105–6107;
r) A. Voituriez, A. Panossian, N. Fleury-Brégeot, P. Retailleau,
A. Marinetti, Adv. Synth. Catal. 2009, 351, 1968–1976; s) N.
Compound 6b: General Procedure G; yield 1.4 mg, 4%; this is a
known compound.[9] 1H NMR (400 MHz, CDCl3, TMS): δ = 3.91
(s, 2 H, CH2), 4.46 (s, 2 H, CH2), 7.32–7.46 (m, 8 H, ArH), 7.51–
7.57 (m, 2 H, ArH), 7.74 (d, J = 7.2 Hz, 2 H, ArH), 7.91 (d, J =
7.2 Hz, 2 H, ArH) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ =
37.4, 40.7, 121.7, 124.0, 126.8, 127.7, 128.0, 128.3, 128.4, 128.5,
131.9, 133.2, 136.4, 139.9, 140.9, 143.4, 144.3, 146.0, 194.9,
195.7 ppm.
Supporting Information (see footnote on the first page of this arti-
cle): Spectroscopic data and chiral HPLC traces of the compounds
(Tables S1, S2, S3, and S4), detailed descriptions of experimental
procedures and crystal structure of 4a.
Acknowledgments
We thank the Shanghai Municipal Committee of Science and Tech-
nology (11JC1402600), the National Basic Research Program of
8
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20940
/KAP1
Date: 20-09-12 15:42:55
Pages: 10
Catalyzed Asymmetric Intramolecular Rauhut–Currier Reactions
Pinto, M. Neel, A. Panossian, P. Retailleau, G. Frison, A. Voit-
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u) F.-R. Zhong, G.-Y. Chen, Y.-X. Lu, Org. Lett. 2011, 13, 82–
85; v) J.-M. Garnier, C. Anstiss, F. Liu, Adv. Synth. Catal. 2009,
351, 331–338; w) C. Anstiss, J.-M. Garnier, F. Liu, Org. Biomol.
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Received: July 17, 2012
Published Online: ᭿
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9

Job/Unit: O20940
/KAP1
Date: 20-09-12 15:42:55
Pages: 10
X.-N. Zhang, M. Shi
FULL PAPER
Asymmetric Organocatalysis
X.-N. Zhang, M. Shi* ..................... 1–10
A
Highly Nucleophilic Multifunctional
Chiral Phosphane-Catalyzed Asymmetric
Intramolecular Rauhut–Currier Reaction
Keywords: Multifunctional chiral phos-
phanes / Rauhut-Currier reaction / Cyclo-
pentene derivatives / Cyclohexene
derivatives / Organocatalysis / Cyclization /
Asymmetric synthesis
A highly nucleophilic multifunctional chi-
ral phosphane enables asymmetric intra-
molecular Rauhut–Currier (RC) reactions
to afford corresponding cyclopentene and
cyclohexene derivatives in moderate to
good yields with good to excellent enantio-
selectivities.
10
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