Iridium-catalyzed asymmetric allylic etherification and ring-closing metathesis reaction for enantioselective synthesis of chromene and 2,5-dihydrobenzo[b]oxepine derivatives

Article abstract of DOI:10.1002/adsc.201100809

Iridium-catalyzed asymmetric etherifications of allylic carbonates with 2-vinylphenols and 2-allylphenols were realized. With a catalyst generated from 2mol% of [Ir(cod)Cl]₂ (cod=cycloocta-1,5-diene) and 4mol% of the phosphoramidite ligand L2, the etherification products were obtained in excellent ees and then subjected to the ring-closing metathesis reaction providing an efficient synthesis of enantioenriched 2H-chromene and 2,5-dihydrobenzo[b]oxepine derivatives. Copyright

Full text of DOI:10.1002/adsc.201100809

FULL PAPERS
DOI: 10.1002/adsc.201100809
Iridium-Catalyzed Asymmetric Allylic Etherification and Ring-
Closing Metathesis Reaction for Enantioselective Synthesis of
Chromene and 2,5-Dihydrobenzo[b]oxepine Derivatives
Hu He,a Ke-Yin Ye,a Qing-Feng Wu,a Li-Xin Dai,a and Shu-Li Youa,*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Lu, Shanghai 200032, Peopleꢀs Republic of China
Fax : (+86)-21-5492-5087; e-mail: slyou@sioc.ac.cn
Received: October 18, 2011; Revised: December 22, 2011; Published online: April 12, 2012
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100809.
Abstract: Iridium-catalyzed asymmetric etherifica- metathesis reaction providing an efficient synthesis
tions of allylic carbonates with 2-vinylphenols and 2- of enantioenriched 2H-chromene and 2,5-dihydro-
allylphenols were realized. With a catalyst generated benzo[b]oxepine derivatives.
from 2 mol% of [IrACHTNUGTRNEUNG(cod)Cl]2 (cod=cycloocta-1,5-
diene) and 4 mol% of the phosphoramidite ligand
L2, the etherification products were obtained in ex- Keywords: allylic substitution; asymmetric catalysis;
cellent ees and then subjected to the ring-closing iridium; ring-closing metathesis
Introduction
chromene derivatives is still rare despite the impor-
tance of these compounds in enantiopure form.[4]
Chromans and chromenes are important structural Therefore, the highly efficient synthesis of enantio-
motifs that exist in numerous natural products and pure chroman and chromene derivatives via asymmet-
drug candidates possessing interesting biological ac- ric catalysis is in great demand.
tivities (Figure 1).[1] Consequently, much attention has
Retrosynthetically, 2H-chromene derivatives could
been paid to their efficient synthesis, and many syn- be accessed via the ring-closing metathesis (RCM) re-
thetic methods for construction of the chroman and action of the ether compounds (I) bearing two termi-
chromene skeletons were reported.[2,3] However, the nal alkenes (Scheme 1). Therefore, an efficient asym-
catalytic asymmetric synthesis of chroman and 2H- metric synthesis of the ether compounds (I) would
represent a key to the success of the above hypothe-
sis. We envisaged that a regio- and enantioselective
allylic etherification of 2-vinylphenols would provide
a straightforward access to enantioenriched ether
compounds (I). It should be noted that the strategy
combining transition metal-catalyzed allyic substitu-
tion and RCM had previously been documented in
the literature.[5–9] Evans and co-workers introduced
the asymmetric allylic amination/RCM strategy to
Figure 1. Selected examples of biologically active chroman
and chromene derivatives.
Scheme 1. A retrosynthetic analysis of enantiopure chro-
mene derivatives.
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Iridium-Catalyzed Asymmetric Allylic Etherification and Ring-Closing Metathesis Reaction
construct the enantioenriched nitrogen-containing tion occurred smoothly providing the ether com-
heterocycles in 1999.[5a] This strategy has also been pounds (I) bearing two terminal alkenes. The prod-
utilized in Pd- and Cu-catalyzed allylic alkylations.[6,7] ucts obtained here were subjected to an RCM reac-
Target-directed synthesis via Ir-catalyzed allylic sub- tion affording enantiopure 2H-chromene derivatives.
stitution/RCM was also extensively explored by In this paper, we report such an efficient synthesis of
Helmchen[8] and many others.[9]
enantioenriched chroman and 2H-chromene deriva-
Transition metal-catalyzed allylic substitution reac- tives via Ir-catalyzed asymmetric etherification with 2-
tions are very powerful tools for constructing carbon- vinylphenols and a subsequent RCM reaction. The
carbon and carbon-heteroatom bonds.[10] The palladi- same strategy was also applied for the synthesis of
um-catalyzed variant generally provides a mixture of enantioenriched 2,5-dihydrobenzo[b]oxepines.
branched and linear products, which often favors the
linear substitution products with limited excep-
tions.[11,12] On the contrary, branched substitution Results and Discussion
products are usually favored for other transition
metals such as Mo,[13] W,[14] Fe,[15] Ru,[16] Rh,[17] Ni,[18] Iridium-Catalyzed Asymmetric Allylic Etherification
Cu,[19] Ir.[20] For the use of substituted phenols as suit- and Ring-Closing Metathesis Reaction for
able nucleophiles in the transition metal-catalyzed al- Enantioselective Synthesis of Chromene Derivatives
lylic substitution reactions it has been documented in
the literature that phenols generally proceed with O- We began our studies by utilizing 2-vinylphenol (1a)
allylation[21–25] with only limited examples of C-allyla- and (E)-3-(4-bromophenyl)allyl methyl carbonate
tion.[26]
(2a) as the model substrates in the Ir-catalyzed allylic
As part of our continued research interests towards substitution reactions. As summarized in Table 1, with
Ir-catalyzed allylic substitution reaction,[27,28] we re- the Ir catalyst generated in situ from 2 mol% of
cently found that the reaction of 2-vinylanilines with [IrACTHNUTRGNEN(UG cod)Cl]2 and 4 mol% of phosphoramidite L1
allylic carbonates under the Ir-catalytic conditions (Figure 2), the reaction of 1a and 2a in the presence
proceeds via an allylic vinylation pathway.[28a,b] When of 1.1 equiv. of K3PO4 in THF gave the desired
2-vinylphenol derivatives were tested under the same branched etherification product in good yield (68%)
Ir-catalytic conditions, the allylic etherification reac- and excellent enantioselectivity (95% ee) although
Table 1. Screening of various bases and additives.[a]
Entry
Base
Yield [%][b]
3aa/4aa[c]
ee [%][d]
1
2
3
4
5
6
7
8
K3PO4
68
48
60
10
36
62
trace
n.r.
n.r.
46
86/14
80/20
85/15
53/47
95/5
82/18
–
95
94
96
95
94
89
–
–
–
93
–
DABCO
Cs2CO3
DBU
LiHMDS
NaHMDS
BSA
Et3N
DIEA
Cs2CO3
Cs2CO3
–
–
9
10[e]
11[f]
89/11
–
trace
[a]
Reaction conditions: 2 mol% of [IrACTHNURTGNENG(U cod)Cl]2, 4 mol% of L1, 0.2 mmol of 1a, 0.2 mmol of 2a and 110 mol% of base in
THF (2 mL).
Isolated yield of 3aa.
Determined by H NMR of the crude reaction mixture.
Determined by HPLC analysis.
100 mol% of CuI was used.
100 mol% of LiI was used.
[b]
[c]
[d]
[e]
[f]
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tained with metal halides[29,30] as the additives in Ir-
catalyzed allylic alkylation reactions, we then exam-
ined several such additives in our case. However, the
reaction with CuI only led to a slightly improved
b/l ratio but a decreased yield (entry 10, Table 1). The
reaction with LiI was very sluggish (entry 11, Table 1).
Next, several readily available chiral phosphorami-
dite ligands were examined with either Cs2CO3 or
K3PO4 as the base. As summarized in Table 2, the re-
actions with different ligands all proceeded smoothly
and the combination of L2 and Cs2CO3 afforded the
best results (entries 1–6, Table 2). The reaction with
Figure 2. Phosphoramidite ligands and Zhan-1B catalyst.
the b (branched)/l (linear) ratio (86/14) is not satisfac- either 0.5 equiv. or 2.0 equiv. of Cs2CO3 led to a de-
tory (entry 1, Table 1). These promising results en- crease of both yield and enantioselectivity (entries 7
couraged us to further test different bases. Examina- and 8, Table 2). Screening various solvents such as
tion of bases such as DABCO, Cs2CO3, DBU, CH2Cl2, toluene, dioxane, DME, and Et2O disclosed
LiHMDS disclosed that varying the base has little that THF is the best solvent for the etherification re-
effect on the enantioselectivity of the etherification action (entries 3, 9–13, Table 2).
product. Cs2CO3 is a good choice of base concerning
After screening the bases, additives, ligands and sol-
both yield and b/l ratio (entries 2–5, Table 1). Slightly vents, we established the optimal reaction conditions
decreased yield, b/l ratio and enantioselectivity were for the Ir-catalyzed enantioselective allylic etherifica-
observed when NaHMDS was employed (entry 6, tion (i.e., 2 mol% of [IrACTHUNRGTNEUNG(cod)Cl]2, 4 mol% of L2,
Table 1). However, the reaction with BSA only gave 110 mol% of Cs2CO3, 0.2 mmol of 1, 0.2 mmol of 2 in
a trace amount of product and the reaction did not THF at 508C, entry 3, Table 2). In addition, we tested
occur at all with Et3N or DIEA (entries 7–9, Table 1). the subsequent RCM reaction of the etherification
Since remarkably improved regioselectivies were ob- products. The following procedure was developed:
Table 2. Screening of various ligands and solvents.[a]
Entry
L
Base
Solvent
Yield [%][b]
3aa/4aa[c]
ee [%][d]
1
2
3
4
5
6
L1
L1
L2
L2
L3
L3
L2
L2
L2
L2
L2
L2
L2
Cs2CO3
K3PO4
Cs2CO3
K3PO4
Cs2CO3
K3PO4
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
THF
THF
THF
THF
THF
THF
THF
THF
CH2Cl2
toluene
dioxane
DME
Et2O
60
68
71
69
57
60
49
60
49
53
69
73
63
85/15
86/14
93/7
89/11
72/28
72/28
85/15
93/7
82/18
83/17
90/10
91/9
96
95
94
95
97
92
90
90
77
90
94
95
88
7[e]
8[f]
9
10
11
12
13
78/22
[a]
Reaction conditions: 2 mol% of [IrACTHNUTRGENUG(N cod)Cl]2, 4 mol% of L, 0.2 mmol of 1a, 0.2 mmol of 2a and 110 mol% of base in THF
(2 mL).
Isolated yield of 3aa.
Determined by H NMR of the crude reaction mixture.
Determined by HPLC analysis.
50 mol% of Cs2CO3 was used.
200 mol% of Cs2CO3 was used.
[b]
[c]
[d]
[e]
[f]
1
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Iridium-Catalyzed Asymmetric Allylic Etherification and Ring-Closing Metathesis Reaction
Table 3. Ir-catalyzed allylic etherification with 2-vinylphenols/RCM reaction.[a]
Entry
1, R1
2, R2
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
1a, H
1a, H
1a, H
1a, H
1a, H
1a, H
1a, H
1b, 4-MeO
1c, 4-Br
1d, 4-Cl
1d, 4-Cl
1e, 6-MeO
2a, 4-Br-C6H4
2b, 4-Me-C6H4
2c, 4-MeO-C6H4
2d, 3-MeO-C6H4
2e, 3-Cl-C6H4
2f, Ph
2g, n-C3H7
2f, Ph
2f, Ph
5aa, 73
5ab, 43
5ac, 41
5ad, 61
5ae, 62
5af, 68
5ag, 52
5bf, 29
5cf, 50
5df, 42
5dh, 39
trace
94
94
86
93
90
94
93
89
92
92
92
-
9
10
11
12
2f, Ph
2h, 4-Cl-C6H4
2c, 4-MeO-C6H4
[a]
Reaction conditions: 1) 2 mol% of [IrACHTNUTRGNEUNG(cod)Cl]2, 4 mol% of L2, 0.2 mmol of 1, 0.2 mmol of 2 and 110 mol% of Cs2CO3 in
THF (2 mL); 2) 2 mol% of Zhan-1B in CH2Cl2.
Isolated yield.
Determined by HPLC analysis.
[b]
[c]
upon completion of the Ir-catalyzed enantioselective Iridium-Catalyzed Asymmetric Allylic Etherification
allylic etherification reaction, the etherification prod- and Ring-Closing Metathesis Reaction for
ucts obtained by short silica gel column chromatogra- Enantioselective Synthesis of 2,5-
phy were then subjected to RCM reaction in the pres- Dihydrobenzo[b]oxepine Derivatives
ence of 2 mol% of Zhan-1B in CH2Cl2 at room tem-
perature (Figure 2).[31]
To further broaden the utility of this synthetic strat-
Following the above optimized procedures, the sub- egy, 2-allylphenols were also tested under the etherifi-
strate scope was explored for various substituted 2-vi- cation/RCM conditions, which would lead to the
nyphenols and allyl methyl carbonates to test the gen- enantioenriched 2,5-dihydrobenzo[b]oxepines. The re-
erality of this methodology. The results are summar- sults are summarized in Table 4. To our delight, fol-
ized in Table 3. Substrates bearing either electron-do- lowing the same two-step procedures, 2,5-dihydroben-
nating groups (4-Me, 4-MeO, 3-MeO, entries 2–4, zo[b]oxepines could be obtained generally in a higher
Table 3) or electron-withdrawing groups (4-Br, 3-Cl, degree of efficiency than the chromene formation
entries 1 and 5, Table 3) on the phenyl ring of the cin- with good yields (49–82%) and excellent ees (93–
namyl cabonates were well tolerated and led to the 96%). Notably, benzo[b]oxepine is the structural
corresponding 2H-chromene derivatives in moderate motif of many natural products and drug candi-
to good yields (41–73%) over two steps with excellent dates.[32]
enantioselectivities (86–94% ee). Notably, aliphatic
allyl methyl carbonate also worked quite well (52%
yield, 93% ee, entry 7, Table 3). In addition, the reac- Transformations of the Products
tions with 2-vinylphenols bearing either an electron-
donating group (4-MeO, entry 8, Table 3) or electron- The application of the products obtained with the cur-
withdrawing groups (4-Br, 4-Cl, entries 9–11, Table 3) rent methodology has been explored. With the enan-
generally led to slightly decreased yields (29–50%) tioenriched chromenes in hand, the chroman scaffold
but excellent enantioselectivities (90–92% ee). How- could be easily obtained by hydrogenation with PtO2
ever, when 6-MeO-2-vinylphenol was used, no reac- in ethyl acetate at room temperature [Eq. (1) and Eq.
tion occurred probably due to the steric hindrance of (2)]. The absolute configuration of 5aa was assigned
the ortho-substitution (entry 12, Table 3).
to be (S) by comparing the optical rotation of the hy-
drogenated product 8.[33] It should be noted that the
hydrogenation product 9 is an inhibitor of rhinovirus
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Table 4. Ir-catalyzed etherification with 2-allylphenols/RCM reaction.[a]
Entry
6, R1
2, R2
Yield [%][b]
ee [%][c]
1
2
3
4
5
6
7
8
9
10
6a, H
6a, H
6a, H
6a, H
6a, H
6a, H
6a, H
6a, H
2a, 4-Br-C6H4
2b, 4-Me-C6H4
2c, 4-MeO-C6H4
2d, 3-MeO-C6H4
2e, 3-Cl-C6H4
2f, Ph
2g, n-C3H7
2h, 4-Cl-C6H4
2f, Ph
7aa, 82
7ab, 63
7ac, 67
7ad, 74
7ae, 61
7af, 81
7ag, 70
7ah, 49
7bf, 70
7cf, 69
96
94
95
95
96
94
94
95
95
93
6b, 4-MeO
6c, 4-Cl
2f, Ph
[a]
Reaction conditions: 1) 2 mol% of [IrACHTNUTRGNEUNG(cod)Cl]2, 4 mol% of L2, 0.2 mmol of 6, 0.2 mmol of 2 and 110 mol% of Cs2CO3 in
THF (2 mL); 2) 2 mol% of Zhan-1B in CH2Cl2.
Isolated yield.
Determined by HPLC analysis.
[b]
[c]
(BW683C).[34] The hydrogenation reactions generally Experimental Section
proceed in excellent yields (91–95%) without notable
loss of the enantiomeric purity.
General Procedure for the Ir-Catalyzed Allylic
Etherification Reaction with 2-Vinylphenols/RCM
Reaction
Conclusions
A flame-dried Schlenk tube was cooled to room tempera-
ture and filled with argon. To this flask were added
In summary, we have successfully developed an effi-
cient method for the synthesis of enantioenriched 2H-
chromene and 2,5-dihydrobenzo[b]oxepine derivatives
by employing Ir-catalyzed asymmetric allylic etherifi-
cation and a subsequent RCM reaction. The current
methodology features high enantioselectivity and
ready availability of the starting materials, which
make it particularly attractive in organic synthesis.
[IrACTHUNTRGNE(UGN cod)Cl]2 (2.7 mg, 0.004 mmol, 2 mol%), phosphoramidite
ligand L2 (5.1 mg, 0.008 mmol, 4 mol%), THF (0.5 mL) and
n-propylamine (0.5 mL). The reaction mixture was heated at
508C for 0.5 h, and the color of the solution changed from
orange to light yellow. Then the reaction mixture was
cooled to room temperature, and the solvent was removed
under vacuum. To the same flask, 2-vinylphenol derivative
1
(0.20 mmol), allylic carbonate
2 (0.2 mmol), Cs2CO3
(71.5 mg, 0.22 mmol) and THF (2 mL) were added. The re-
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Iridium-Catalyzed Asymmetric Allylic Etherification and Ring-Closing Metathesis Reaction
action mixture was stirred at 508C for 24 h. After the reac-
tion was complete (monitored by TLC), the crude reaction
mixture was filtered through celite and washed with EtOAc.
The solvents were removed under reduced pressure. Then
the crude residue was purified by silica gel column chroma-
tography to give the products (branched products 3 and
linear products 4).
To a solution of the above products in CH2Cl2 (3 mL) was
added Zhan-1B catalyst (2.9 mg, 0.004 mmol) under an
argon atmosphere. The mixture was stirred at room temper-
ature for 4 h. Then the solvent was removed under reduced
pressure. The residue was purified by silica gel column chro-
matography to afford the desired products 5.
5ac:[36] Colorless oil; yield: 41%; 86% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
230 nm, t(minor)=28.80 min, t
(major)=35.26 min]; [a]2D0:
À126.5 (c 0.40, CH2Cl2); H NMR (300 MHz, CDCl3): d=
3.80 (s, 3H), 5.78 (dd, J=9.9, 3.3 Hz, 1H), 5.86–5.87 (m,
1H), 6.54 (dd, J=9.9, 1.5 Hz, 1H), 6.75 (d, J=7.8 Hz, 1H),
6.83–6.90 (m, 3H), 7.01 (d, J=7.5 Hz, 1H), 7.09 (t, J=
7.8 Hz, 1H), 7.38 (d, J=8.4 Hz, 2H).
N
ACHTUNGTRENNUNG
1
5ad: Colorless oil; yield: 61%; 93% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
230 nm,
t
(minor)=5.04 min,
tACTHNGUTERNNUG
(major)=5.57 min]; [a]2D0:
1
À154.6 (c 1.50, CH2Cl2); H NMR (400 MHz, CDCl3): d=
3.79 (s, 3H), 5.78 (dd, J=10.0, 3.2 Hz, 1H), 5.88–5.89 (m,
1H), 6.50–6.53 (m, 1H), 6.79 (d, J=8.0 Hz, 1H), 6.84–6.88
(m, 2H), 6.99–7.04 (m, 3H), 7.08–7.14 (m, 1H), 7.23–7.30
(m, 1H); 13C NMR (100 MHz, CDCl3): d=55.2, 77.0, 112.5,
113.8, 116.0, 119.2, 121.2, 121.3, 124.0, 124.8, 126.6, 129.4,
129.7, 142.4, 153.1, 159.8; IR (thin film): nmax =3041, 2937,
3aa: Colorless oil; yield: 71%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=99/1, v=0.6 mLminÀ1, l=
(major)=13.47 min]; [a]2D0:
254 nm, tACHTUNGTRENNUNG(minor)=12.00 min, tHCATUNGTRENNUGN
+69.0 (c 1.00, CHCl3); 1H NMR (400 MHz, CDCl3): d=
5.25–5.30 (m, 2H), 5.34 (d, J=17.2 Hz, 1H), 5.60 (d, J=
5.6 Hz, 1H), 5.75 (dd, J=17.6, 1.2 Hz, 1H), 6.06 (ddd, J=
16.4, 10.4, 6.0 Hz, 1H), 6.78 (d, J=8.4 Hz, 1H), 6.92 (t, J=
7.6 Hz, 1H), 7.09–7.18 (m, 2H), 7.28 (d, J=8.4 Hz, 2H),
7.48 (d, J=8.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
80.6, 114.4, 114.5, 116.9, 121.3, 121.7, 126.5, 127.7, 128.3,
2834, 1733, 1601, 1487, 1455, 1272, 1040, 778, 753, 699 cmÀ1
;
MS (EI): m/z=238 (M+); HR-MS (EI): m/z=238.0998,
calcd. for C16H14O2 (M+): 238.0994.
5ae: Colorless oil; yield: 62%; 90% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
128.5, 131.5, 131.8, 137.5, 139.2, 154.6. IR (thin film): nmax
=
230 nm,
t
(minor)=4.37 min,
tACTHNGUTERNNUG
(major)=4.86 min]; [a]2D0:
1
3085, 1900, 1626, 1598, 1485, 1454, 1291, 1234, 1106, 1072,
1011, 993, 931, 813, 749 cmÀ1; MS (EI): m/z=314 (M+); HR-
MS (EI): m/z=314.0301, calcd. for C17H15OBr (M+):
314.0306..
À222.2 (c 1.30, CH2Cl2); H NMR (400 MHz, CDCl3): d=
5.77 (dd, J=10.0, 3.6 Hz, 1H), 5.88–5.90 (m, 1H), 6.55 (d,
J=9.6 Hz, 1H), 6.80 (d, J=8.4 Hz, 1H), 6.88 (t, J=7.6 Hz,
1H), 7.01 (d, J=7.6 Hz, 1H), 7.12 (t, J=9.6 Hz, 1H), 7.29–
7.45 (m, 4H); 13C NMR (100 MHz, CDCl3): d=76.3, 116.0,
121.1, 121.4, 124.0, 124.4, 125.1, 126.7, 127.2, 128.4, 129.6,
129.9, 134.5, 142.8, 152.8; IR (thin film): nmax =2959, 1738,
1693, 1485, 1350, 1229, 1113, 1078, 775 cmÀ1; MS (EI): m/z=
242 (M+); HR-MS (EI): m/z=242.0500, calcd. for
C15H11OCl (M+): 242.0498.
4aa: 1H NMR (400 MHz, CDCl3): d=4.69 (dd, J=5.6,
1.6 Hz, 2H), 5.28 (dd, J=11.2, 1.2 Hz, 1H), 5.76 (dd, J=
18.0, 1.6 Hz, 1H), 6.41 (dt, J=16.0, 5.6 Hz, 1H), 6.66 (d, J=
16.0 Hz, 1H), 6.89 (d, J=8.0 Hz, 1H), 6.95 (t, J=7.6 Hz,
1H), 7.12 (dd, J=18.0, 11.2 Hz, 1H), 7.20–7.28 (m, 3H),
7.43–7.47 (m, 2H), 7.48–7.51 (m, 2H); 13C NMR (100 MHz,
CDCl3) d 68.8, 112.4, 114.5, 121.0, 121.6, 125.4, 126.5, 127.1,
128.1, 128.8, 131.3, 131.5, 131.7, 135.4, 155.6; IR (thin film):
nmax =2856, 1625, 1596, 1486, 1447, 1236, 1108, 1071, 1008,
972, 909, 752 cmÀ1; MS (EI): m/z=314 (M+); HR-MS (EI):
m/z=314.0308, calcd. for C17H15OBr (M+): 314.0306.
5aa: Colorless oil; yield: 73%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=99/1, v=1.0 mLminÀ1, l=
5af:[37] Colorless oil; yield: 68%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=0.6 mLminÀ1, l=
(major)=32.45 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(minor)=29.13 min, tHCATUNGTRENNUNG
1
À144.2 (c 0.66, CH2Cl2); H NMR (300 MHz, CDCl3): d=
5.80 (dd, J=9.6, 3.3 Hz, 1H), 5.91–5.93 (m, 1H), 6.53 (dd,
J=9.6, 1.2 Hz, 1H), 6.89 (d, J=8.1 Hz, 1H), 6.86 (t, J=
8.1 Hz, 1H), 7.01 (d, J=7.8 Hz, 1H), 7.11 (t, J=7.8 Hz,
1H), 7.32–7.47 (m, 5H).
(major)=20.12 min]; [a]2D0:
254 nm, tACHTUNGTRENNUNG(minor)=17.68 min, tHCATUNGTRENNUGN
À215.3 (c 1.00, CHCl3); 1H NMR (400 MHz, CDCl3): d=
5.75 (dd, J=10.0, 3.2 Hz, 1H), 5.85–5.86 (m, 1H), 6.53 (dd,
J=10.0, 2.0 Hz, 1H), 6.77 (d, J=8.4 Hz, 1H), 6.86 (t, J=
7.2 Hz, 1H), 7.00 (dd, J=7.2, 2.0 Hz, 1H), 7.10 (t, J=
8.0 Hz, 1H), 7.31 (d, J=8.4 Hz, 2H), 7.48 (d, J=8.4 Hz,
2H); 13C NMR (100 MHz, CDCl3): d=76.2, 116.0, 121.1,
121.3, 122.3, 124.1, 124.4, 126.6, 128.7, 129.6, 131.7, 139.7,
152.8; IR (thin film): nmax =3044, 2926, 1738, 1630, 1604,
5ag:[38] Colorless oil; yield: 52%; 93% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=99/1, v=1.0 mLminÀ1, l=
230 nm,
t
(minor)=5.67 min,
tACTHNGUTERNNUG
(major)=6.65 min]; [a]2D0:
1
À176.2 (c 0.85, CH2Cl2); H NMR (400 MHz, CDCl3): d=
0.95 (t, J=7.6 Hz, 3H), 1.43–1.85 (m, 4H), 4.84–4.86 (m,
1H), 5.87 (dd, J=4.8, 3.2 Hz, 1H), 6.38 (d, J=10.0 Hz, 1H),
6.77 (d, J=8.0 Hz, 1H), 6.83 (t, J=7.2 Hz, 1H), 6.95 (d, J=
7.6 Hz, 1H), 7.09 (t, J=9.2 Hz, 1H).
1589, 1263, 1228, 1205, 1114, 1011, 958, 824, 798, 753 cmÀ1
;
5bf:[39] Colorless oil; yield: 29%; 89% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=70/30, v=1.0 mLminÀ1, l=
MS (EI): m/z=285 (M+); HR-MS (EI): m/z=285.9995,
calcd. for C15H11OBr (M+): 285.9993.
(major)=44.26 min]; [a]2D0:
254 nm, tACTHNUGRTENNUG(minor)=32.62 min, tHCATUNGTRENNUNG
1
5ab:[35] Colorless oil; yield: 43%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
À224.8 (c 0.70, CH2Cl2); H NMR (300 MHz, CDCl3): d=
3.76 (s, 3H), 5.83–5.88 (m, 2H), 6.49–6.75 (m, 4H), 7.26–
7.46 (m, 5H).
(major)=32.50 min]; [a]2D0:
230 nm, tACHTUNGTRENNUNG(minor)=18.72 min, tHCATUNGTRENNUGN
À192.0 (c 0.89, CH2Cl2); 1H NMR (300 MHz, CDCl3) d=
2.34 (s, 3H), 5.78 (dd, J=9.9, 3.6 Hz, 1H), 5.87–5.88 (m,
1H), 6.53 (d, J=9.9 Hz, 1H), 6.76 (d, J=7.8 Hz, 1H), 6.85
(t, J=7.5 Hz, 1H), 7.01 (d, J=7.5 Hz, 1H), 7.09 (t, J=
7.8 Hz, 1H), 7.17 (d, J=7.8 Hz, 2H), 7.34 (d, J=8.1 Hz,
2H).
5cf:[37] Colorless oil; yield: 50%; 92% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=70/30, v=1.0 mL·minÀ1, l=
(major)=19.48 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(minor)=16.55 min, tHCATUNGTRENNUGN
1
À151.4 (c 1.30, CH2Cl2); H NMR (400 MHz, CDCl3): d=
5.84 (dd, J=10.0, 3.6 Hz, 1H), 5.90–5.92 (m, 1H), 6.47 (dd,
J=9.6, 1.6 Hz, 1H), 6.66 (d, J=8.0 Hz, 1H), 7.12 (d, J=
Adv. Synth. Catal. 2012, 354, 1084 – 1094
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1089

Hu He et al.
FULL PAPERS
2.4 Hz, 1H), 7.18 (dd, J=8.8, 2.8 Hz, 1H), 7.33–7.43 (m,
5H).
1H), 5.48–5.56 (m, 2H), 5.96–6.02 (m, 1H), 6.87–6.90 (m,
1H), 7.00 (t, J=8.8 Hz, 1H), 7.11 (t, J=7.2 Hz, 2H), 7.17
(d, J=8.4 Hz, 2H), 7.31 (d, J=8.4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=21.2, 31.4, 82.3, 122.6, 123.9, 126.1,
127.6, 127.7, 128.4, 129.1, 130.5, 136.5, 137.4, 137.9, 157.0; IR
(thin film): nmax =3407, 3023, 2921, 1605, 1514, 1488, 1232,
968, 799 cmÀ1; MS (EI): m/z=236 (M+); HR-MS (EI):
m/z=236.1206, calcd. for C17H16O (M+): 236.1201.
5df:[37] Colorless oil; yield: 42%; 92% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=97/3, v=1.0 mLminÀ1, l=
(major)=23.18 min]; [a]2D0:
230 nm, tACHTUNGTRENNUNG(minor)=20.75 min, tHCATUNGTRENNUNG
1
À243.1 (c 1.00, CH2Cl2); H NMR (300 MHz, CDCl3): d=
5.83–5.92 (m, 2H), 6.48 (d, J=9.9 Hz, 1H), 6.71 (d, J=
9.0 Hz, 1H), 6.99 (d, J=2.7 Hz, 1H), 7.04 (dd, J=8.4,
2.4 Hz, 1H), 7.33–7.44 (m, 5H).
7ac: Colorless oil; yield: 67%; 95% ee [Daicel Chiralcel
5dh:[40] Colorless oil; yield: 39%; 92% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=70/30, v=1.0 mLminÀ1, l=
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
(minor)=40.10 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(major)=26.40 min, tHCATUNGTRENNUGN
(major)=10.55 min]; [a]2D0:
tACHTUNGTRENNUNG(minor)=8.03 min, tACTHUNGTRENNUGN
1
1
230 nm,
À110.4 (c 0.85, CH2Cl2); H NMR (400 MHz, CDCl3): d=
3.33 (dd, J=16.8, 6.4 Hz, 1H), 3.76–3.80 (m, 1H), 3.80 (s,
3H), 5.50–5.55 (m, 2H), 5.97–6.03 (m, 1H), 6.84–6.89 (m,
3H), 6.99 (t, J=7.6 Hz, 1H), 7.08–7.11 (m, 2H), 7.32 (d, J=
8.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=31.4, 55.3,
82.0, 113.7, 122.7, 123.9, 126.2, 127.6, 128.4, 129.2, 130.4,
132.5, 136.5, 156.8, 159.5; IR (thin film): nmax =3400, 2933,
2836, 1610, 1512, 1248, 1175, 1055, 801, 776 cmÀ1; MS (EI):
m/z=252 (M+); HR-MS (EI): m/z=252.1154, calcd. for
C17H16O2 (M+): 252.1150; anal. calcd. for C17H16O2: C 80.93,
H 6.39; found: C 80.90, H 6.35.
À145.2 (c 1.00, CH2Cl2); H NMR (300 MHz, CDCl3): d=
5.80–5.88 (m, 2H), 6.49 (d, J=9.9 Hz, 1H), 6.70 (d, J=
8.4 Hz, 1H), 6.99–7.07 (m, 2H), 7.34–7.36 (m, 2H).
General Procedure for the Ir-Catalyzed Allylic
Etherification with 2-Allylphenols/RCM Reaction
A flame-dried Schlenk tube was cooled to room tempera-
ture and filled with argon. To this flask were added [Ir-
ACHTUNGTRENNUNG(cod)Cl]2 (2.7 mg, 0.004 mmol, 2 mol%), phosphoramidite
ligand L2 (5.1 mg, 0.008 mmol, 4 mol%), THF (0.5 mL) and
n-propylamine (0.5 mL). The reaction mixture was heated at
508C for 0.5 h, and the color of the solution changed from
orange to light yellow. Then the reaction mixture was
cooled to room temperature, and the solvent was removed
under vacuum. To the same flask, 2-vinylphenol derivative 6
7ad: Colorless oil; yield: 74%; 95% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
(minor)=32.57 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(major)=22.31 min, tHCATUNGTRENNUGN
1
À131.9 (c 1.00, CH2Cl2); H NMR (400 MHz, CDCl3): d=
3.27 (dd, J=16.8, 6.8 Hz, 1H), 3.80 (S, 3H), 3.83–3.89 (m,
1H), 5.47–5.57 (m, 2H), 5.96–6.02 (m, 1H), 6.87 (dd, 8.0,
2.8 Hz, 1H), 6.92 (d, J=8.0 Hz, 1H), 6.98–7.03 (m, 3H),
7.10–7.14 (m, 2H), 7.24–7.30 (m, 1H); 13C NMR (100 MHz,
CDCl3): d=31.4, 55.2, 82.3, 113.0, 113.8, 119.9, 122.5, 124.0,
126.2, 127.7, 128.4, 129.4, 130.4, 136.3, 142.0, 157.0, 159.7; IR
(thin film): nmax =3395, 2936, 2834, 1600, 1488, 1454, 1266,
1232, 1197, 1048, 886, 767 cmÀ1; MS (EI): m/z=252 (M+);
HR-MS (EI): m/z=252.1155, calcd for C17H16O2 (M+):
252.1150.
(0.20 mmol), allylic carbonate
2
(0.2 mmol), Cs2CO3
(71.5 mg, 0.22 mmol) and THF (2 mL) were added. The re-
action mixture was stirred at 508C for 24 h. After the reac-
tion was complete (monitored by TLC), the crude reaction
mixture was filtered through celite and washed with EtOAc.
The solvents were removed under reduced pressure. Then
the crude residue was purified by silica gel column chroma-
tography to give the products.
To a solution of the above products in CH2Cl2 (3 mL) was
added Zhan-1B catalyst (2.9 mg, 0.004 mmol) under an
argon atmosphere. The mixture was stirred at room temper-
ature for 4 h. Then the solvent was removed under reduced
pressure. The residue was purified by silica gel column chro-
matography to afford the desired products 7.
7ae: Colorless oil; yield: 61%; 96% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
(minor)=11.24 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(major)=10.27 min, tCAHTUNGTRENNGUN
1
À126.2 (c 0.94, CH2Cl2); H NMR (400 MHz, CDCl3): d=
3.26 (dd, J=16.8, 6.8 Hz, 1H), 3.82–3.89 (m, 1H), 5.46–5.53
(m, 2H), 5.98–6.04 (m, 1H), 6.91 (d, J=7.6 Hz, 1H), 7.02 (t,
J=8.0 Hz, 1H), 7.11–7.15 (m, 2H), 7.28–7.29 (m, 3H), 7.44
(s, 1H); 13C NMR (100 MHz, CDCl3): d=31.4, 81.7, 122.4,
124.2, 125.7, 126.8, 127.8, 128.2, 128.6, 129.6, 129.7, 134.3,
136.2, 142.4, 156.8; IR (thin film): nmax =3023, 1598, 1488,
1298, 1232, 1078, 946, 785, 692 cmÀ1; MS (EI): m/z=256
(M+); HR-MS (EI): m/z=256.0653, calcd. for C16H13OCl
(M+): 256.0655; anal. calcd. for C16H13OCl: C 74.85, H 5.10;
found: C 74.87, H 5.06.
7aa: Colorless oil; yield: 82%; 96% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=95/5, v=1.0 mLminÀ1, l=
(minor)=19.52 min]; [[a]2D0:
230 nm, tACHTUNGTRENNUNG(major)=11.22 min, tHCATUNGTRENNUGN
À77.3 (c 2.20, CH2Cl2); 1H NMR (400 MHz, CDCl3): d=
3.32 (dd, J=16.8, 6.8 Hz, 1H), 3.80 (dd, J=16.8, 4.0 Hz,
1H), 5.47–5.52 (m, 2H), 5.98–6.04 (m, 1H), 6.85 (d, J=
9.2 Hz, 1H), 7.01 (t, J=8.4 Hz, 1H), 7.11 (t, J=8.0 Hz, 2H),
7.27 (t, J=8.8 Hz, 2H), 7.47–7.50 (m, 2H); 13C NMR
(75 MHz, CDCl3): d=31.4, 81.6, 122.1, 122.5, 124.1, 126.7,
127.7, 128.5, 129.4, 129.7, 131.5, 136.2, 139.3, 156.6; IR (thin
film): nmax =3022, 1585, 1488, 1453, 1425, 1263, 1231, 1102,
1011, 965, 789 cmÀ1; MS (EI): m/z=300 (M+); HR-MS (EI):
m/z=300.0149, calcd for C16H13OBr (M+): 300.0150; anal.
calcd. for C16H13OBr: C 63.81, H 4.35; found: C 63.92, H
4.65.
7af: Colorless oil; yield: 81%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
(major)=19.32 min]; [a]2D0:
230 nm, tACTHNUGRTENNUG(minor)=17.72 min, tHCATUNGTRENNUNG
1
À102.6 (c 1.02, CH2Cl2); H NMR (400 MHz, CDCl3): d=
3.28 (dd, J=16.8, 6.8 Hz, 1H), 3.86 (d, J=16.8 Hz, 1H),
5.52–5.57 (m, 2H), 5.97–6.02 (m, 1H), 6.89 (d, J=8.0 Hz,
1H), 7.01 (d, J=7.2 Hz, 1H), 7.09–7.13 (m, 2H), 7.29–7.43
(m, 5H); 13C NMR (100 MHz, CDCl3): d=31.4, 82.4, 122.5,
124.0, 126.2, 127.7, 128.1, 128.3, 128.4, 130.4, 136.4, 140.4,
157.0; IR (thin film): nmax =3023, 1598, 1488, 1298, 1232,
1078, 946, 785, 692 cmÀ1); MS (EI): m/z=222 (M+); HR-MS
(EI): m/z=222.1039, calcd. for C16H14O (M+): 222.1045;
7ab: Colorless oil; yield: 63%; 94% ee [Daicel Chiralcel
OJ-H, hexane/2-propanol=85/15, v=1.0 mLminÀ1, l=
(minor)=24.53 min]; [a]2D0:
230 nm, tACHTUNGTRENNUNG(major)=11.76 min, tCAHTUNGTRENNGUN
1
À128.6 (c 0.86, CH2Cl2); H NMR (400 MHz, CDCl3): d=
2.35 (s, 3H), 3.29 (dd, J=16.8, 6.8 Hz, 1H), 3.81–3.86 (m,
1090
asc.wiley-vch.de
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 1084 – 1094

Iridium-Catalyzed Asymmetric Allylic Etherification and Ring-Closing Metathesis Reaction
anal. calcd. for C16H14O: C 86.45, H 6.35; found: C 86.25, H
6.46.
alpak
AS-H,
hexane/2-propanol=99.75/0.25,
v=
0.6 mLminÀ1, l=254 nm, t
G
ACHTUNGTRENNUNG
1
7ag: Colorless oil; yield: 70%; 94% ee [Daicel Chiralcel
13.33 min]; [a]2D0: À18.7 (c 0.50, CHCl3); H NMR (300 MHz,
CDCl3): d=2.02–2.25 (m, 2H), 2.79 (dt, J=16.2, 4.8 Hz,
1H), 3.00 (ddd, J=16.8, 10.5, 5.4 Hz, 1H), 5.06 (dd, J=9.9,
2.4 Hz, 1H), 6.85–6.93 (m, 2H), 7.08–7.15 (m, 2H), 7.29–
7.44 (m, 4H); 13C NMR (100 MHz, CDCl3): d=25.1, 29.9,
77.7, 116.9, 120.3, 121.8, 126.0, 127.3, 127.8, 128.5, 129.5,
141.7, 155.1. m.p.: 62–648C.
OJ-H, hexane/2-propanol=90/10, v=0.6 mLminÀ1, l=
(major)=8.71 min]; [a]2D0: +4.4
220 nm, tACHTUNGTRENNUNG(minor)=7.70 min, tHCATUNGTRENNUGN
(c 0.82, CH2Cl2); 1H NMR (400 MHz, CDCl3): d=0.99 (t,
J=7.2 Hz, 3H), 1.56–1.81 (m, 4H), 3.10 (dd, J=16.8, 7.2 Hz,
1H), 3.78 (d, J=19.2 Hz, 1H), 4.41–4.42 (m, 1H), 5.40 (d,
J=11.2 Hz, 1H), 5.80–5.85 (m, 1H), 6.97–7.18 (m, 4H);
13C NMR (100 MHz, CDCl3): d=13.9, 18.8, 31.6, 38.1, 80.1,
121.9, 123.6, 125.7, 127.7, 128.6, 131.5, 136.0, 157.7; IR (thin
film): nmax =3390, 2958, 2930, 1645, 1487, 1452, 1253, 1233,
1109, 980 cmÀ1; MS (EI): m/z=188 (M+); HR-MS (EI):
m/z=188.1205, calcd. for C13H16O (M+): 188.1201.
9:[34] Starting from product 5dh by following the general
procedure; colorless oil; yield: 95%; 90% ee [Daicel Chiral-
cel OJ-H, hexane/2-propanol=70/30, v=1.0 mLminÀ1, l=
230 nm,
(major)=10.78 min]; [a]2D0:
tACHTUNGTERNGN(UN minor)=6.87 min, tACTHUNGTRENNUGN
1
À3.2 (c 1.0, CHCl3); H NMR (300 MHz, CDCl3): d=1.98–
2.07 (m, 1H), 2.14–2.23 (m, 1H), 2.71–2.79 (m, 1H), 2.90–
3.01 (m, 1H), 5.01 (dd, J=9.9, 2.4 Hz, 1H), 6.81–6.91 (m,
3H), 7.31–7.40 (m, 4H).
7ah: Colorless oil; yield: 49%; 95% ee [Daicel Chiralpak
IC, hexane/2-propanol=99/1, v=0.6 mLminÀ1, l=220 nm,
tN
t
A
1
0.60, CH2Cl2); H NMR (400 MHz, CDCl3): d=1.41 (d, J=
6.8 Hz, 3H), 3.18 (dd, J=16.8, 6.8 Hz, 1H), 3.71 (dd, J=
16.8, 6.4 Hz, 1H), 4.60–4.63 (m, 1H), 5.37–5.41 (m, 1H),
5.78–5.84 (m, 1H), 6.98–7.19 (m, 4H); 13C NMR (100 MHz,
CDCl3): d=22.0, 31.4, 76.3, 122.2, 123.7, 125.2, 127.6, 128.6,
132.3, 136.1, 157.2; IR (thin film): nmax =2962, 1454, 1412,
1260, 1094, 802 cmÀ1; MS (EI): m/z=160 (M+); HR-MS
(EI): m/z=160.0886, calcd for C11H12O (M+): 160.0888.
7bf: Colorless oil; yield: 70%; 95% ee [Daicel Chiralpak
IC, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=230 nm,
Acknowledgements
We thank National Basic Research Program of China (973
Program 2010CB833300) and the NSFC (20821002,
20923005, 20932008, 21025209) for generous financial sup-
port.
tG
N
1
0.73, CH2Cl2); H NMR (300 MHz, CDCl3): d=3.22 (dd, J=
16.5, 6.9 Hz, 1H), 3.76 (s, 3H), 3.84 (d, J=16.5 Hz, 1H),
5.46–5.56 (m, 2H), 5.95–6.03 (m, 1H), 6.60–6.67 (m, 2H),
6.82 (d, J=8.4 Hz, 1H), 7.32–7.43 (m, 5H); 13C NMR
(100 MHz, CDCl3): d=31.5, 55.5, 82.7, 111.7, 114.0, 122.9,
125.9, 127.7, 128.1, 128.4, 130.5, 137.5, 140.4, 150.6, 155.7; IR
(thin film): nmax =2962, 1454, 1412, 1260, 1094, 802 cmÀ1; MS
(EI): m/z=252 (M+); HR-MS (EI): m/z=252.1154, calcd.
for C17H16O2 (M+): 252.1150.
References
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(Eds.), Chromans and Tocopherols, in: The Chemistry
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7cf: Colorless oil; yield: 69%; 93% ee [Daicel Chiralcel
OD-H, hexane/2-propanol=90/10, v=1.0 mLminÀ1, l=
230 nm,
t
(major)=4.57 min,
tACTHNGUTERNNUG
(minor)=4.86 min]; [a]2D0:
1
À124.0 (c 0.67, CH2Cl2); H NMR (300 MHz, CDCl3): d=
3.29 (dd, J=16.5, 6.0 Hz, 1H), 3.77 (d, J=18.9 Hz, 1H),
5.51–5.58 (m, 2H), 5.95–6.03 (m, 1H), 6.77 (d, J=8.1 Hz,
1H), 7.04–7.11 (m, 2H), 7.35–7.39 (m, 5H); 13C NMR
(100 MHz, CDCl3): d=31.0, 82.4, 123.8, 125.6, 127.4, 127.8,
128.3, 128.5, 128.8, 130.3, 138.1, 139.7, 155.3; IR (thin film):
nmax =3028, 2927, 2852, 1655, 1482, 1452, 1426, 1239, 1173,
1056, 1027, 1002, 879, 821 cmÀ1; MS (EI): m/z=256 (M+);
HR-MS (EI): m/z=256.0653, calcd. for C16H13OCl (M+):
256.0655..
General Procedure for the Hydrogenation of 5
To a solution of 5aa (28.6 mg, 0.10 mmol) in EtOAc (2 mL)
was added 10% PtO2 (2.3 mg, 0.01 mmol) under an argon at-
mosphere. Then the reactor was charged with 1 atm of H2
and the reaction mixture was stirred at room temperature.
After 5aa had been fully consumed (monitored by TLC),
the reaction mixture was filtered through a celite pad. After
removal of the solvent, the residue was purified by silica gel
column chromatography (n-hexane/EtOAc=150/1) to give 8
as yellow solid; yield: 26.2 mg (91%); 94% ee [Daicel Chir-
Adv. Synth. Catal. 2012, 354, 1084 – 1094
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
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