Iridium-catalyzed enantioselective allylic alkylation of methyl 2-(4-nitrophenylsulfonyl)acetate and subsequent transformations

Article abstract of DOI:10.1002/adsc.201200113

Highly enantioselective allylic alkylation reactions of methyl 2-(4-nitrophenylsulfonyl)acetate were carried out in the presence of an iridium catalytic system. The subsequent transformations of the products including reductive desulfonylation and modifie

Full text of DOI:10.1002/adsc.201200113

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DOI: 10.1002/adsc.201200113
Iridium-Catalyzed Enantioselective Allylic Alkylation of Methyl
2-(4-nitrophenylsulfonyl)acetate and Subsequent Transformations
Qing-Long Xu,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: February 10, 2012; Revised: April 14, 2012; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200113.
Abstract: Highly enantioselective allylic alkylation products of methyl acetate or methyl acrylate with
reactions of methyl 2-(4-nitrophenylsulfonyl)acetate good yields and high enantioselectivity.
were carried out in the presence of an iridium cata-
lytic system. The subsequent transformations of the
products including reductive desulfonylation and Keywords: allylic alkylation; asymmetric catalysis;
modified Julia olefination led to the allylic alkylation iridium; sulfones
Introduction
of their products,[2] we envisaged that the Ir-catalyzed
asymmetric allylic alkylation reaction of methyl sul-
Sulfone functionalities can be easily removed by re- fone acetates would provide a class of interesting
duction or transformed into other useful functional products. After straightforward transformations, the
groups, and sulfonyl compounds also serve as key in- allylic alkylation product of methyl acetate or the
termediates in organic synthesis.[1] As a consequence, alkene could be accessed. As part of our ongoing pro-
much attention has been paid to the employment of gram on Ir-catalyzed allylic substitution reactions,[8]
sulfonyl compounds as nucleophiles in various trans- we recently realized the Ir-catalyzed enantioselective
fomations, including many catalytic asymmetric reac- allylic alkylation of methyl 2-(4-nitrophenylsulfonyl)-
tions.[2,3] The recent emergence of organocatalysis has
ACHTUNGTRENaNGNU cetate. The highly enantioenriched alkylation prod-
enabled various asymmetric reactions utilizing b-car- ucts could be subjected to the reductive desulfonyla-
bonyl sulfones as carbon nucleophiles that could be tion and a modified Julia olefination reaction to form
easily converted to alkynyl, alkenyl, and carbonyl C=C bonds.[9] Herein, we report our studies on this
functionalities.[2] Transition metal-catalyzed asymmet- subject.
ric allylic alkylation reactions have been demonstrat-
ed as an efficient tool for the formation of carbon-
carbon bonds.[4] Particularly, reactions catalyzed by Results and Discussion
chiral iridium complexes provide great regio- and
enantioselectivities when terminally monosubstituted At the outset, methyl 2-(4-nitrophenylsulfonyl)acetate
allylic substrates are used.[5] The scope of carbon nu- 1 and allyl carbonate 2a were used as model sub-
cleophiles was highly broadened recently.[6] Despite strates. The Ir-catalytic system including [Ir
ACTHNUTRGNEG(NU cod)Cl]2,
the progress being made in the Ir-catalyzed allylic phosphoramidite L1 (Figure 1), and n-propylamine as
alkylation reaction, the direct utilization of unsubsti- activator, a protocol developed by Hartwig and co-
tuted methyl acetate or an alkene as nucleophile has workers,[10] was used as the catalyst. In the presence
been rarely explored. With a palladium catalyst, Trost of 2 mol% of [IrACTHUNRGTNEUNG(cod)Cl]2, 4 mol% of L1, and
and Hou, respectively, reported the use of imidazoyl 100 mol% of Cs2CO3, the reaction of methyl 2-(4-ni-
ketones and acylsilanes as nucleophiles in allylic trophenylsulfonyl)acetate 1 and allyl carbonate 2a in
alkylation reactions to afford esters with excellent THF for 6 h gave alkylation product 3a in 76% yield
enantioselectivity after transformation.[7] Inspired by with a 97/3 branched to linear ratio (entry 1, Table 1).
the recent application of b-carbonyl sulfones in orga- The epimerization at the a-position of the carbonyl
nocatalytic reactions and the versatile transformations group resulted in the poor diastereoselectivity of the
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Figure 1. Ligands used in the present work.
products. However, this chiral center could be elimi- 78% yield with a 94/6 b/l, and 95% ee for 4a (entry 7,
nated during the transformation. Subjecting product Table 1).
3a to a reductive desulfonylation reaction afforded
Under the above conditions (entry 7, Table 1), vari-
product 4a, the ee of which was determined to be ous solvents such as THF, CH2Cl2, toluene, CH3CN,
94%. Various bases including K3PO4, K2CO3, KOAc, ether, DME, dioxane, and DCE were examined. As
Et3N, DIEA, BSA, DBU, and DABCO could all be summarized in Table 2, all the tested solvents were
utilized in the reaction affording excellent branched able to give excellent enantioselectivity with variable
to linear ratios and enantioselectivity (89–96% ee, en- yields. The highest yield (94%) was obtained in re-
tries 2–9, Table 1). Taking the enantioselectivity, dia- fluxing CH2Cl2 (entry 2, Table 2). Notably, the reac-
stereoselectivity and yield into account, BSA was tion in CH2Cl2 at room temperature afforded product
chosen as the optimal base, affording product 3a in 3a in 88% yield and 93% ee (entry 9, Table 2).
Table 1. Screening of bases.[a]
Entry
Base
Time [h]
b/l (dr)[b]
Yield [%][c]
ee of 4a [%][d]
1
2
3
4
5
6
7
8
9
Cs2CO3
K3PO4
K2CO3
KOAc
Et3N
DIEA
BSA
DBU
6
97/3 (2.0/1)
84/16 (1.7/1)
90/10 (1.9/1)
91/9 (1.7/1)
93/7 (2.0/1)
91/9 (1.7/1)
94/6 (1.7/1)
94/6 (1.7/1)
87/13 (1.8/1)
76
62
84
42
34
54
78
38
78
94
94
95
96
96
93
95
93
89
12
18
12
24
20
12
24
18
DABCO
[a]
Reaction conditions: 2 mol% of [IrACTHNURTGNENG(U cod)Cl]2, 4 mol% of L1, 0.4 mmol of 1, 0.4 mmol of 2a and 100 mol% base in THF
(4 mL).
[b]
[c]
[d]
1
Determined by H NMR of the crude reaction mixture.
Isolated yield of 3a.
Determined by HPLC analysis. BSA=N,O-bis(trimethylsilyl)acetamide.
2
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Iridium-Catalyzed Enantioselective Allylic Alkylation of Methyl 2-(4-nitrophenylsulfonyl)acetate
Table 2. Screening of solvents.[a]
Entry
Solvent
Time [h]
Temperature [oC]
b/l (dr)[b]
Yield [%][c]
ee of 4a [%][d]
1
2
3
4
5
6
7
8
9
THF
12
3
20
20
8
20
20
20
4
50
reflux
50
50
reflux
50
50
50
r.t.
94/6 (1.7/1)
96/4 (1.7/1)
92/8 (1.7/1)
92/8 (2.5/1)
94/6 (2.7/1)
93/7 (1.9/1)
92/8 (1.7/1)
94/6 (2.2/1)
94/6 (1.4/1)
78
94
80
57
86
62
23
74
88
95
94
97
68
94
93
96
94
93
CH2Cl2
toluene
MeCN
Et2O
DME
dioxane
DCE
CH2Cl2
[a]
Reactions were conducted under the conditions of entry 7, Table 1.
Determined by H NMR of the crude reaction mixture.
Isolated yield of 3a.
Determined by HPLC analysis.
[b]
[c]
[d]
1
Table 3. Screening of ligands.[a]
were carried out, namely reductive desulfonylation
and a modified Julia olefination (HCHO, Cs2CO3,
DMF, 08C to room temperature). The results are
summarized in Table 4. Aryl allylic carbonates bear-
ing an electron-donating group such as p-Me, p-OMe,
or m-OMe could be well tolerated with 96/4–99/
1 branched to linear ratios and 89–97% ee (entries 2–
4, Table 4). Unfortunately, the reaction of 1-naphthyl
allylic carbonate 2e gave poor selectivity due to the
steric bulkiness (entry 5, Table 4). Aryl allylic carbo-
nates bearing an electron-withdrawing group such as
p-Br, p-F, p-CF3, or m-Cl could also been tolerated
(entries 6–9, Table 4). Subjecting 1-thienyl allylic car-
bonate 2j under the optimized reaction conditions led
to the two types of products including reductive de-
sulfonylation and modified Julia olefination in excel-
lent selectivity, respectively (95/5 b/l, 96% ee,
entry 10, Table 4). Reaction of aliphatic allylic car-
Entry
Ligand
Time
[h]
b/l
Yield
[%][c]
ee of 4a
(dr)[b]
[%][d]
1
2
3
4
5
6
7
8
L1
L2
L3
L4
L5
L6
L7
L8
3
6
6
8
8
8
8
8
96/4 (1.7/1)
96/4 (3.0/1)
96/4 (2.1/1)
60/40 (1.7/1)
94/6 (1.7/1)
95/5 (1.6/1)
60/40 (1.7/1)
71/29 (2.0/1)
94
96
97
5
18
38
33
85
94
95
91
ND
72
-86
66
58
[a]
Reactions were conducted under the conditions of
entry 2, Table 2.
Determined by H NMR of the crude reaction mixture.
Isolated yield of 3a.
Determined by HPLC analysis.
[b]
[c]
[d]
1
Next, different ligands were evaluated (Figure 1), bonate 2k also occurred in good yield and high enan-
and the results are summarized in Table 3. Ligands L2 tioselectivity (93% ee) with moderate regioselectivity
and L3 could be employed in the reaction, giving (entry 11, Table 4).
comparable results with those obtained with ligand
The absolute configuration of product 4a was deter-
L1 (entries 1–3, Table 3). Notably, ligand L2 afforded mined to be (S) by comparing the sign of its optical
the product with slightly improved enantioselectivity rotation with that reported in the literature.[12] Prod-
(95% ee).[11] The catalyst derived from L6, a diastereo- uct (S)-4a could be easily converted to g-lactone (R)-
isomer of L1, could catalyze the reaction in a lower 6 through ozonolysis and reductive work-up (NaBH4,
yield and enantioselectivity (38% yield, À86% ee, MeOH) [Eq. (1)]. The g-lactone 6 was obtained in
entry 6, Table 3). Several other ligands were tested in
the reaction, and none of them provided better re-
sults. Overall, the optimized reaction conditions were
chosen
as
the
following:
2 mol%
of
[Ir(cod)Cl]2, 4 mol% of L2, 1.0 equiv. of BSA,
ACHTUNGTRENNUNG
CH2Cl2, reflux. Notably, when cinnamyl acetate was 94% ee, indicating that there is almost no loss of
used under the optimized conditions, a low conversion enantiopurity during these transformations.
was obtained but with similar selectivities (35% con-
version after 24 h, b/l: 99/1, dr: 2.0/1).
With the optimized reaction conditions in hand, the Conclusions
scope of the Ir-catalyzed enantioselective allylic
alkylation of methyl 2-(4-nitrophenylsulfonyl)acetate In summary, we have found that methyl 2-(4-
was examined. Two tranformations of the products nitrophenACHTUNTRGNEUNGylsulfonyl)acetate could be utilized in Ir-cat-
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Table 4. Substrate scope.[a]
Entry
2
b/l[b]
4
Yield [%][c]
ee [%][d]
5
Yield [%][c]
ee [%][d]
1
2
3
4
5
6
7
8
2a
2b
2c
2d
2e
2f
2g
2h
2i
96/4
97/3
99/1
96/4
98/2
94/6
97/3
89/11
92/8
95/5
75/25
4a
4b
4c
4d
4e
4f
4g
4h
4i
68
55
66
60
59
63[e]
68
61
62
69
64
95
94
93
89
30
5a
5b
5c
5d
5e
5f
5g
5h
5i
82
66
80
72
71
77
82
74
75
83
77
90
93
97
95
25
94
96
[f]
–
95
88
[f]
-
[f]
9
10
11
–
91
96
2j
2k
4j
4k
96
93
5j
5k
[f]
-
[a]
Reactions were conducted under the conditions of entry 2, Table 3.
Determined by H NMR of the crude reaction mixture.
Isolated yield over two steps.
Determined by HPLC analysis (the ee of 4k was determined by GC).
Product containing debromination by-product.
HPLC analysis was unsuccessful.
[b]
[c]
[d]
[e]
[f]
1
sulfonyl)acetate 1 (103.6 mg, 0.40 mmol), N,O-bis(trimethyl-
silyl)acetamide (81.2 mg, 0.40 mmol, 100 mol%) and CH2Cl2
(4.0 mL) were added. The reaction mixture was stirred
under reflux until the carbonate was fully consumed, as
monitored by TLC or 1H NMR. Then the crude reaction
mixture was filtered with celite and washed by EtOAc. The
solvents were removed under reduced pressure. The ratio of
regioisomers (branched to linear=b/l) was determined from
alyzed enantioselective allylic alkylation reactions.
Under the optimized reaction conditions, the alkyla-
tion reactions proceeded to give good to excellent
branched to linear ratios and enantioselectivity for
a wide range of substrates. The one-pot transforma-
tions of the alkylation products via reductive desulfo-
nylation and a modified Julia olefination led to two
classes of useful enantioenriched products, respective-
ly. Further application of the current synthetic strat-
egy and products towards pharmaceutical compounds
and key intermediates are ongoing in our laboratory.
1
the H NMR spectrum of the crude reaction mixture. The
crude residue was purified by silica gel column chromatog-
raphy (petroleum ether/ethyl acetate: 10/1) to give the de-
sired products.
To a flask containing the above alkylation product in dry
CH3OH (10 mL) under argon at 08C, Mg powder (30 equiv.)
was added. The suspension was allowed to warm slowly to
room temperature and stirred overnight under argon. The
reaction mixture was then quenched with saturated aqueous
NH4Cl (10 mL) and extracted with Et2O (3ꢂ10 mL). The
combined organic phases were evaporated, and the residue
was purified by silica gel column chromatography (petrole-
um ether/ethyl acetate: 20/1).
Experimental Section
General Procedure for Ir-Catalyzed Enantioselective
Allylic Alkylation of Methyl 2-(4-nitrophenylsul-
fonyl)acetate and Reductive Desulfonylation
[IrACHTUNGTRENNUNG(cod)Cl]2 (0.008 mmol, 2 mol%) and phosphoramidite
4a, colorless oil, yield: 68% yield, b/l: 96/4, ee: 95%
[Daicel CHIRALCEL OB-H (0.46 cmꢂ25 cm); n-hexane/2-
propanol=95/5; flow rate=0.7 mL·minÀ1; detection wave-
length=214 nm]: tR =8.92 (major), 9.84 (minor) min, [a]2D0:
ligand L2 (0.016 mmol, 4 mol%) were dissolved in THF
(1 mL) and n-propylamine (0.6 mL) in a dry Schlenk tube
filled with argon. The reaction mixture was heated at 508C
for 30 min and then the volatile solvents were removed
under vacuum to give a yellow solid. After that, allylic car-
bonate 2 (0.40 mmol, 100 mol%), methyl 2-(4-nitrophenyl-
1
À7.5 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.32–
7.19 (m, 5H), 5.97 (ddd, J=7.2, 10.2, 17.1 Hz, 1H), 5.09–
4
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Iridium-Catalyzed Enantioselective Allylic Alkylation of Methyl 2-(4-nitrophenylsulfonyl)acetate
5.03 (m, 2H), 3.87 (appq, J=7.5 Hz, 1H), 3.60 (s, 3H), 2.81–
2.65 (m, 2H); 13C NMR (75 MHz, CDCl3): d=172.2, 142.3,
140.1, 128.5, 127.4, 126.6, 114.7, 51.5, 45.4, 40.0.
4f, colorless oil, yield: 63%, b/l: 94/6 (product containing
debromination by-product 4a), [a]2D0: À8.0 (c 0.5, CHCl3).
1H NMR (300 MHz, CDCl3): d=7.43 (d, J=8.4 Hz, 1H),
7.33–7.20 (m, 2H), 7.08 (d, J=8.4 Hz, 1H), 6.04–5.87 (m,
1H), 5.10–5.02 (m, 2H), 3.91–3.80 (m, 1H), 3.62 (s, 3H),
2.82–2.65 (m, 2H); 13C NMR (75 MHz, CDCl3): d=172.3,
172.0, 142.4, 141.3, 140.2, 139.6, 131.6, 129.3, 128.6, 127.5,
126.7, 120.5, 115.2, 114.8, 51.65, 51.57, 45.5, 44.8, 40.0, 39.8;
IR (film): vmax =2952, 1739, 1489, 1436, 1257, 1265, 1011,
920, 701 cmÀ1; EI-MS: m/z (rel. int.)=268 (M+, 18), 210
(16), 195 (16), 129 (80), 116 (100); HR-MS (EI): m/z=
268.0096, calcd. for C12H13O2Br [M]+: 268.0099.
4b, colorless oil, yield: 55%, b/l: 97/3, ee: 94% [Daicel
CHIRALPAK AS-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.5 mL·minÀ1
;
detection wave-
length=214 nm]: tR =10.13 (minor), 12.21 (major) min,
1
[a]2D0: À8.2 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=
7.10 (m, 4H), 5.96 (ddd, J=7.2, 10.2, 17.1 Hz, 1H), 5.06 (d,
J=15.9 Hz, 1H), 5.04 (d, J=11.4 Hz, 1H), 3.83 (appq, J=
7.5 Hz, 1H), 3.61 (s, 3H), 2.79–2.63 (m, 2H), 2.31 (s, 3H);
13C NMR (75 MHz, CDCl3): d=172.3, 140.4, 139.4, 136.2,
4g, colorless oil, yield: 68%, b/l: 97/3, ee: 95% [Daicel
CHIRALPAK AS-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
129.2, 127.3, 114.6, 51.5, 45.1, 40.1, 21.0; IR (film): vmax
=
3082, 2951, 2922, 1740, 1514, 1257, 1163, 918, 815; EI-MS
(m/z): 204 (M+, 48), 144 (46), 131 (100), 115 (32), 91 (27),
77 cmÀ1 (6); HR-MS (EI): m/z=204.1153, calcd. for
C13H16O2 [M]+: 204.1150.
nol=90/10; flow rate=0.7 mL·minÀ1
;
detection wave-
length=214 nm]: tR =6.88 (minor), 8.92 (major) min, [a]2D0:
1
À14.9 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.16
(dd, J=5.1, 8.7 Hz, 2H), 6.99 (t, J=8.7 Hz, 2H), 5.96 (ddd,
J=6.6, 10.2, 17.4 Hz, 1H), 5.05 (d, J=10.2 Hz, 1H), 5.05 (d,
J=17.4 Hz, 1H), 3.86 (appq, J=7.2 Hz, 1H), 3.62 (s, 3H),
2.80–2.63 (m, 2H); 13C NMR (75 MHz, CDCl3): d=172.2,
161.6 (d, J=243 Hz), 140.0, 137.9 (d, J=3.5 Hz), 129.0 (d,
J=8.0 Hz), 115.4 (d, J=21.2 Hz), 114.9, 51.7, 44.7, 40.1;
19F NMR (282 MHz, CDCl3): d=À116.7 (m); IR (film):
4c, colorless oil, yield: 66%, b/l: 99/1, ee: 93% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10, flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =5.87 (major), 6.50 (minor) min, [a]2D0:
1
À12.3 (c 0.4, CHCl3). H NMR (300 MHz, CDCl3): d=7.12
(d, J=8.7 Hz, 2H), 6.84 (d, J=8.7 Hz, 2H), 5.96 (ddd, J=
6.9, 10.8, 16.5 Hz, 1H), 5.06 (d, J=10.2 Hz, 1H), 5.03 (d, J=
16.5 Hz, 1H), 3.83 (appq, J=7.5 Hz, 1H), 3.79 (s, 3H), 3.62
(s, 3H), 2.79–2.61 (m, 2H); 13C NMR (75 MHz, CDCl3): d=
172.4, 158.2, 140.4, 134.4, 128.4, 114.5, 113.9, 55.2, 51.6, 44.6,
40.2; IR (film): vmax =3000, 2952, 2836, 1738, 1611, 1512,
1249, 1035, 831; EI-MS (m/z): 220 (M+, 40), 160 (13), 147
(100), 132 (8), 115 (20), 91 cmÀ1 (25); HR-MS (EI): m/z=
220.1100, calcd. for C13H16O3 [M]+: 220.1099.
v
max =2953, 2921, 1739, 1059, 1223, 1159, 834; EI-MS (m/z):
208 (M+, 28), 148 (60), 135 (100), 109 cmÀ1 (36); HR-MS
(EI): m/z=208.0898, calcd. for C12H13OF [M]+: 208.0900.
4h, colorless oil, yield: 61%, b/l: 89/11, ee: 88% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=98/2; flow rate=0.7 mL·minÀ1; detection wavelength=
214 nm]: tR =10.05 (minor), 10.70 (major) min, [a]2D0: À4.7 (c
0.5, CHCl3). 1H NMR (400 MHz, CDCl3): d=7.56 (d, J=
8.0 Hz, 2H), 7.33 (d, J=8.0 Hz, 2H), 5.96 (ddd, J=7.2, 10.4,
17.2 Hz, 1H), 5.12 (d, J=8.7 Hz, 1H), 5.08 (d, J=12.9 Hz,
1H), 3.94 (appq, J=7.2 Hz, 1H), 3.63 (s, 3H), 2.80 (dd, J=
7.6, 15.2 Hz, 1H), 2.71 (dd, J=7.6, 15.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=171.9, 146.4, 139.3, 129.2, 127.9, 125.5
(q, J=3.0 Hz), 115.7, 51.7, 45.2, 39.7; 19F NMR (376 MHz,
CDCl3): d=À61.8 (s); IR (film): vmax =2955, 1740, 1618,
1327, 1165, 1124, 1069, 1018, 841 cmÀ1; EI-MS: m/z (rel.
int.)=258 (M+, 18), 198 (100), 185 (80), 165 (44), 129 (56),
115 (30); HR-MS (EI): m/z=258.0865, calcd. for C13H13O2F3
[M]+: 258.0868.
4d, colorless oil, yield: 60%, b/l: 96/4, ee: 89% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =6.37 (major), 8.72 (minor) min, [a]2D0:
1
À13.7 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.26–
7.20 (m, 1H), 6.82–6.75 (m, 3H), 5.97 (ddd, J=7.2, 10.2,
17.1 Hz, 1H), 5.08 (d, J=16.2 Hz, 1H), 5.07 (d, J=10.2 Hz,
1H), 3.85 (appq, J=7.5 Hz, 1H), 3.79 (s, 3H), 3.63 (s, 3H),
2.81–2.66 (m, 2H); 13C NMR (100 MHz, CDCl3): d=172.3,
159.7, 144.1, 140.0, 129.6, 119.8, 114.9, 113.4, 111.8, 55.1,
51.6, 45.5, 40.0; IR (film): vmax =3000, 2952, 2836, 1738,
1600, 1489, 1436, 1262, 1162, 1046, 920 cmÀ1; EI-MS: m/z
(rel. int.)=220 (M+, 68), 160 (100), 147 (78), 129 (37), 115
(43), 91 (45); HR-MS (EI): m/z=220.1098, calcd. for
C13H16O3 [M]+: 220.1099.
4i, colorless oil, yield: 62%, b/l: 92/8, [a]2D0: À10.8 (c 0.5,
1
CHCl3). H NMR (300 MHz, CDCl3): d=7.26–7.08 (m, 4H),
5.94 (ddd, J=7.2, 10.2, 17.1 Hz, 1H), 5.11 (d, J=10.2 Hz,
1H), 5.08 (d, J=17.1 Hz, 1H), 3.85 (appq, J=7.5 Hz, 1H),
3.63 (s, 3H), 2.76 (dd, J=7.5, 15.3 Hz, 1H), 2.67 (dd, J=7.5,
15.3 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=172.0, 144.4,
139.4, 134.3, 129.8, 127.7, 126.9, 125.8, 115.5, 51.7, 45.1, 39.8;
IR (film): vmax =2951, 1739, 1434, 1255, 1165, 785 cmÀ1; EI-
MS: m/z (rel. int.)=224 (M+, 20), 151 (42), 129 (100), 115
(54); HR-MS (EI): m/z=224.0606, calcd. for C12H13O2Cl
[M]+: 224.0604.
4e, colorless oil, yield: 59%, b/l: 98/2, ee: 30% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =13.54 (minor), 14.96 (major) min,
1
[a]2D0: À15.8 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=
8.17 (d, J=8.4 Hz, 1H), 7.86 (d, J=7.8 Hz, 1H), 7.75 (d, J=
8.4 Hz, 1H), 7.57–7.34 (m, 4H), 6.12 (ddd, J=6.6, 10.5,
16.8 Hz, 1H), 5.16 (d, J=9.6 Hz, 1H), 5.14 (d, J=18.3 Hz,
1H), 4.75 (appq, J=7.2 Hz, 1H), 3.65 (s, 3H), 2.90 (d, J=
7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=172.5, 139.7,
138.4, 134.0, 131.2, 128.9, 127.4, 126.1, 125.6, 125.4, 124.1,
123.3, 115.4, 51.7, 40.3, 39.7; IR (film): vmax =3047, 2950,
1737, 1435, 1166, 919, 778; EI-MS: m/z (rel. int.)=240 (M+,
12), 179 (15), 165 (100), 152 cmÀ1 (42); HR-MS (EI): m/z=
240.1153, calcd. for C16H16O2 [M]+: 240.1150.
4j, colorless oil, yield: 69%, b/l: 95/5, ee: 96% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=80/20; flow rate=0.5 mL·minÀ1
;
detection wave-
length=214 nm]: tR =5.96 (major), 7.29 (minor) min, [a]2D0:
1
+18.7 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.17
(d, J=5.1 Hz, 1H), 6.95–6.92 (m, 1H), 6.85 (d, J=3.6 Hz,
1H), 5.97 (ddd, J=7.5, 10.2, 17.1 Hz, 1H), 5.16 (d, J=
17.1 Hz,1H), 5.12 (d, J=10.2 Hz, 1H), 4.16 (appq, J=
Adv. Synth. Catal. 0000, 000, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
5
ÞÞ
These are not the final page numbers!

Qing-Long Xu et al.
FULL PAPERS
7.2 Hz, 1H), 3.66 (s, 3H), 2.85–2.71 (m, 2H); 13C NMR
(100 MHz, CDCl3): d=171.8, 146.0, 139.5, 126.8, 123.9,
123.8, 115.6, 51.7, 41.1, 40.9; IR (film): vmax =3459, 3081,
2951, 1739, 1638, 1436, 1167, 991, 923, 698 cmÀ1; EI-MS: m/z
(rel. int.)=196 (M+, 44), 136 (48), 123 (100), 97 (18); HR-
MS (EI): m/z=196.0559, calcd. for C10H12O2S [M]+:
196.0558.
4k, colorless oil, yield: 64%, b/l: 75/25, ee: 93% (deter-
mined by GC) [DEX.CB; 60(2)-150(10); 12.0 psi]: tR =17.42
(minor), 17.55 (major) min, [a]2D0: À5.7 (c 0.5, CHCl3).
1H NMR (400 MHz, CDCl3): d=5.66–5.57 (m, 1H), 5.02 (d,
J=15.6 Hz, 1H), 4.99 (d, J=8.4 Hz, 1H), 3.65 (s, 3H), 2.40–
2.25 (m, 2H), 1.95 (appq, J=7.2 Hz, 1H), 1.38–1.26 (m,
2H), 0.90–0.85 (m, 3H); 13C NMR (100 MHz, CDCl3): d=
173.8, 173.1, 141.1, 131.7, 128.0, 114.9, 51.5, 51.4, 40.2, 40.0,
1H), 6.08 (ddd, J=6.6, 10.2, 17.1 Hz, 1H), 5.56 (s, 1H), 5.16
(d, J=10.2 Hz, 1H), 4.93 (d, J=17.1 Hz, 1H), 4.61 (d, J=
6.6 Hz, 1H), 3.79 (s, 3H), 3.69 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=167.2, 158.2, 142.6, 139.1, 132.5, 129.4, 125.9,
116.3, 113.7, 55.2, 51.9, 49.3; IR (film): vmax =3002, 2952,
2836, 1724, 1609, 1510, 1249, 1137, 1036, 921, 826 cmÀ1; EI-
MS: m/z (Re. int.)=232 (M+, 40), 173 (100), 158 (44), 115
(28), 91 (14); HR-MS (EI): m/z=232.1103, calcd. for
C14H16O3 [M]+: 232.1099.
5d, colorless oil, yield: 72%, b/l: 96/4, ee: 95% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =5.38 (major), 6.04 (minor) min, [a]2D0:
1
+120.5 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.23
(t, J=7.8 Hz, 1H), 6.81–6.74 (m, 3H), 6.37 (s, 1H), 6.08
(ddd, J=6.6, 9.9, 16.8 Hz, 1H), 5.58 (s, 1H), 5.18 (d, J=
9.9 Hz, 1H), 4.97 (d, J=16.8 Hz, 1H), 4.64 (d, J=6.6 Hz,
1H), 3.79 (s, 3H), 3.70 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=167.1, 159.6, 142.35, 142.28, 138.7, 129.3, 126.3,
36.7, 34.6, 34.2, 27.9, 22.5, 20.1, 14.0, 13.6; IR (film): vmax
=
2954, 2921, 1740, 1436, 1164, 1081, 1018 cmÀ1; EI-MS: m/z
(rel. int.)=156 (M+, 3), 124 (32), 113 (48), 96 (78), 82 (52),
74 (54), 55 (100); HR-MS (EI): m/z=156.1148, calcd. for
C9H16O2 [M]+: 156.1150.
120.9, 116.7, 114.3, 111.8, 55.1, 51.9, 50.1; IR (film): vmax
=
3002, 2951, 2835, 1724, 1599, 1489, 1437, 1252, 1140, 1050,
776 cmÀ1; EI-MS: m/z (rel. int.)=232 (M+, 80), 200 (43), 173
(100), 158 (74), 141 (66), 129 (58), 115 (62), 91 (20); HR-MS
(EI): m/z=232.1102, calcd. for C14H16O3 [M]+: 232.1099.
5e, colorless oil, yield: 71%, b/l: 98/2, ee: 25% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
General Procedure for Modified Julia Olefination
To a solution of the alkylation product in DMF (4 mL) at
08C, aqueous formaldehyde (114 mL, 37% w/w solution,
1.5 mmol) and Cs2CO3 (246 mg, 0.75 mmol) were added sep-
arately. The resulting red suspension was allowed to warm
to room temperature, stirred overnight, and then poured
into 10% Na2CO3/H2O (ca. 3:1). The aqueous phase was ex-
tracted with Et2O (3ꢂ10 mL). The combined organic ex-
tracts were dried over MgSO4, filtered and evaporated
under reduced pressure. The product 5 was obtained after
silica gel column chromatography (petroleum ether/ethyl
acetate: 20/1).
nol=90/10; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =5.38 (major), 10.13 (minor) min, [a]2D0:
À8.2 (c 0.5, CHCl3). 1H NMR (300 MHz, CDCl3): d=8.02
(d, J=7.8 Hz, 1H), 7.85 (d, J=7.2 Hz, 1H), 7.75 (d, J=
7.8 Hz, 1H), 7.53–7.32 (m, 4H), 6.37 (s, 1H), 6.18 (ddd, J=
6.3, 10.2, 17.1 Hz, 1H), 5.52 (d, J=6.3 Hz, 1H), 5.43 (s, 1H),
5.27 (d, J=10.2 Hz, 1H), 5.00 (d, J=17.1 Hz, 1H), 3.73 (s,
3H); 13C NMR (100 MHz, CDCl3): d=167.4, 142.1, 138.2,
136.9, 134.0, 131.5, 128.7, 127.5, 127.1, 126.1, 125.6, 125.2,
123.8, 117.3, 52.1, 45.1; IR (film): vmax =2950, 1720, 1509,
1437, 1254, 1136, 776 cmÀ1; EI-MS: m/z (rel. int.)=252 (M+,
31), 193 (90), 178 (44), 165 (100), 152 (32); HR-MS (EI):
m/z=252.1151, calcd. for C17H16O2 [M]+: 252.1150.
5a, colorless oil, yield: 82%, b/l: 96/4, ee: 90% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=80/20; flow rate=0.5 mL·minÀ1
;
detection wave-
length=230 nm]: tR =11.38 (minor), 13.38 (major) min,
1
[a]2D0: +98.1 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=
5f, colorless oil, yield: 77%, b/l: 94/6, ee: 94% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
7.33–7.18 (m, 5H), 6.37 (s, 1H), 6.10 (ddd, J=6.9, 10.2,
17.1 Hz, 1H), 5.58 (s, 1H), 5.18 (d, J=10.2 Hz, 1H), 4.94 (d,
J=17.1 Hz, 1H), 4.66 (d, J=6.9 Hz, 1H), 3.69 (s, 3H).
5b, colorless oil, yield: 66%, b/l: 97/3, ee: 93% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =13.13 (minor), 14.21 (major) min,
[a]2D0: +131.9 (c 0.5, CHCl3). 1H NMR (300 MHz, CDCl3):
d=7.42 (d, J=8.4 Hz, 2H), 7.07 (d, J=8.4 Hz, 2H), 6.39 (s,
1H), 6.06 (ddd, J=6.6, 10.2, 16.8 Hz, 1H), 5.61 (s, 1H), 5.20
(d, J=10.2 Hz, 1H), 4.92 (d, J=16.8 Hz, 1H), 4.61 (d, J=
6.6 Hz, 1H), 3.69 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
166.9, 141.9, 139.7, 138.3, 131.5, 130.2, 126.5, 120.5, 117.1,
52.0, 49.6; IR (film): vmax =3082, 2950, 1724, 1627, 1486,
1436, 1248, 1138, 1011, 923, 816 cmÀ1; EI-MS: m/z (rel.
int.)=280 (M+, 12), 201 (22), 169 (26), 141 (100), 115 (64);
HR-MS (EI): m/z=280.0095, calcd. for C13H13O2Br [M]+:
280.0099.
nol=80/20; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =10.16 (minor), 11.32 (major) min,
[a]2D0: +107.6 (c 0.5, CHCl3). 1H NMR (300 MHz, CDCl3):
d=7.13–7.06 (m, 4H), 6.35 (s, 1H), 6.08 (ddd, J=6.9, 10.2,
17.4 Hz, 1H), 5.57 (s, 1H), 5.16 (d, J=10.2 Hz, 1H), 4.95 (d,
J=17.4 Hz, 1H), 4.62 (d, J=6.9 Hz, 1H), 3.69 (s, 3H), 2.32
(s, 3H); 13C NMR (75 MHz, CDCl3): d=167.2, 142.6, 139.1,
137.6, 136.2, 129.1, 128.3, 126.1, 116.4, 51.9, 49.7, 21.0; IR
(film): vmax =3082, 2951, 1725, 1627, 1512, 1436, 1249, 1137,
920, 813 cmÀ1; EI-MS: m/z (rel. int.)=216 (M+, 32), 201
(68), 157 (100), 141 (100), 115 (61), 91 (37); HR-MS (EI):
m/z=216.1151, calcd. for C14H16O2 [M]+: 216.1150.
5g, colorless oil, yield: 82%, b/l: 97/3, ee: 96% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=90/10; flow rate=0.7 mL·minÀ1
;
detection wave-
5c, colorless oil, yield: 80%, b/l: 99/1, ee: 97% [Daicel
CHIRALCEL OJ-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
length=230 nm]: tR =11.08 (minor), 11.96 (major) min,
[a]2D0: +106.7 (c 0.5, CHCl3). 1H NMR (300 MHz, CDCl3):
d=7.18–7.13 (m, 2H), 6.99 (t, J=8.4 Hz, 2H), 6.37 (s, 1H),
6.07 (ddd, J=6.3, 10.2, 17.1 Hz, 1H), 5.58 (s, 1H), 5.19 (d,
J=10.2 Hz, 1H), 4.92 (d, J=17.1 Hz, 1H), 4.64 (d, J=
nol=80/20; flow rate=0.6 mL·minÀ1
;
detection wave-
length=230 nm]: tR =13.54 (minor), 16.13 (major) min,
1
[a]2D0: +90.4 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=
7.10 (d, J=8.4 Hz, 2H), 6.84 (d, J=8.4 Hz, 2H), 6.34 (s,
6
asc.wiley-vch.de
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
ÝÝ
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Iridium-Catalyzed Enantioselective Allylic Alkylation of Methyl 2-(4-nitrophenylsulfonyl)acetate
6.3 Hz, 1H), 3.69 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
167.0, 161.6 (d, J=243 Hz), 142.3, 138.7, 136.2 (d, J=
3.0 Hz), 129.9 (d, J=8.0 Hz), 126.3, 116.8, 115.2 (d, J=
21.2 Hz), 52.0, 49.3; 19F NMR (282 MHz, CDCl3): d=À116.9
(m); IR (film): vmax =2952, 1724, 1507, 1437, 1249, 1138,
831 cmÀ1; EI-MS: m/z (rel. int.)=220 (M+, 30), 188 (29), 161
(100), 146 (70), 133 (74), 109 (28); HR-MS (EI): m/z=
220.0903, calcd. for C13H13O2F [M]+: 220.0900.
the resulting mixture was subjected to reductive work-up by
adding NaBH4 (12.0 mg, 0.3 mmol). The product 6 was ob-
tained as a white solid after silica gel column chromatogra-
phy (petroleum ether/ethyl acetate: 10/1); yield: 80%; 94%
ee [Daicel CHIRALPAK AD-H (0.46 cmꢂ25 cm); n-
hexane/2-propanol=95/5; flow rate=0.5 mL·minÀ1; detec-
tion wavelength=230 nm], tR =29.97 (major), 28.04 (minor)
1
min, [a]2D0: À35 (c 0.3, CHCl3). H NMR (300 MHz, CDCl3):
5h, colorless oil, yield: 74%, b/l: 89/11, [a]2D0: +99.6 (c 0.5,
d=7.40–7.22 (m, 5H), 4.68 (t, J=8.4 Hz, 1H), 4.28 (t, J=
8.4 Hz, 1H), 3.85–3.74 (m, 1H), 2.94 (dd, J=9.0, 17.4 Hz,
1H), 2.68 (dd, J=9.3, 17.4 Hz, 1H).
1
CHCl3). H NMR (400 MHz, CDCl3): d=7.55 (d, J=8.0 Hz,
2H), 7.31 (d, J=8.0 Hz, 2H), 6.42 (s, 1H), 6.08 (ddd, J=6.8,
10.4, 17.2 Hz, 1H), 5.65 (s, 1H), 5.23 (d, J=10.4 Hz, 1H),
4.94 (d, J=17.2 Hz, 1H), 4.71 (d, J=6.8 Hz, 1H), 3.69 (s,
3H); 13C NMR (100 MHz, CDCl3): d=166.7, 144.9, 141.7,
138.1, 128.3, 125.6, 125.3 (q, J=3.7 Hz), 124.1 (q, J=
270 Hz), 117.5, 52.0, 50.0; 19F NMR (376 MHz, CDCl3): d=
À62.4 (s); IR (film): vmax =2954, 1725, 1617, 1326, 1251,
1124, 1068, 1019 cmÀ1; EI-MS: m/z (rel. int.)=270 (M+, 38),
238 (40), 209 (78), 191 (76), 141 (100), 115 (52); HR-MS
(EI): m/z=270.0870, calcd. for C14H13O2F3 [M]+: 270.0868.
5i, colorless oil, yield: 75%, b/l: 92/8, ee: 91% [Daicel
CHIRALPAK AS-H (0.46 cmꢂ25 cm); hexanes/2-propa-
nol=98/2; flow rate=0.7 mL·minÀ1; detection wavelength=
230 nm], tR =7.19 (minor), 7.72 (major) min, [a]2D0: +104.0 (c
Acknowledgements
We thank National Basic Research Program of China (973
Program 2010CB833300) and the NSFC (20923005,
20932008, 21025209, 21121062) for generous financial sup-
port.
References
1
[1] For a review, see: A. El-Awa, M. N. Noshi, X. M. Jour-
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[2] Selected examples: a) C. Cassani, L. Bernardi, F. Fini,
A. Ricci, Angew. Chem. 2009, 121, 5804–5807; Angew.
Chem. Int. Ed. 2009, 48, 5694–5697; b) M. W. Paix¼o, N.
Holub, C. Vila, M. Nielsen, K. A. Jørgensen, Angew.
Chem. 2009, 121, 7474–7478; Angew. Chem. Int. Ed.
2009, 48, 7338–7342; c) M. Nielsen, C. B. Jacobsen,
M. W. Paix¼o, N. Holub, K. A. Jørgensen, J. Am.
Chem. Soc. 2009, 131, 10581–10586; d) M. Nielsen,
C. B. Jacobsen, N. Holub, M. W. Paix¼o, K. A. Jørgen-
sen, Angew. Chem. 2010, 122, 2726–2738; Angew.
Chem. Int. Ed. 2010, 49, 2668–2679; e) C. B. Jacobsen,
M. Nielsen, D. Worgull, T. Zweifel, E. Fisker, K. A.
Jørgensen, J. Am. Chem. Soc. 2011, 133, 7398–7404.
[3] For examples on a-halosulfones, see: a) T. Fukuzumi,
N. Shibata, M. Sugiura, H. Yasui, S. Nakamura, T.
Toru, Angew. Chem. 2006, 118, 5095–5099; Angew.
Chem. Int. Ed. 2006, 45, 4973–4977; b) S. Mizuta, N.
Shibata, Y. Goto, T. Furukawa, S. Nakamura, T. Toru,
J. Am. Chem. Soc. 2007, 129, 6394–6395.
[4] For reviews: a) B. M. Trost, Chem. Rev. 1996, 96, 395–
422; b) B. M. Trost, M. L. Crawley, Chem. Rev. 2003,
103, 2921–2944; c) Z. Lu, S. Ma, Angew. Chem. 2008,
120, 264–303; Angew. Chem. Int. Ed. 2008, 47, 258–297;
d) S. Fçrster, G. Helmchen, U. Kazmaier, in: Catalytic
Asymmetric Synthesis, 3rd edn., (Ed.: I. Ojima), Wiley,
New Jersey, 2010, p 497.
[5] For reviews, see: a) H. Miyabe, Y. Takemoto, Synlett
2005, 1641–1655; b) R. Takeuchi, S. Kezuka, Synthesis
2006, 3349–3366; c) G. Helmchen, A. Dahnz, P. Dꢃbon,
M. Schelwies, R. Weihofen, Chem. Commun. 2007,
675–691; d) G. Helmchen, in: Iridium Complexes in Or-
ganic Synthesis, (Eds.: L. A. Oro, C. Claver), Wiley-
VCH, Weinheim, Germany, 2009, pp211–250; e) J. F.
Hartwig, L. M. Stanley, Acc. Chem. Res. 2010, 43,
1461–1475; f) J. F. Hartwig, M. J. Pouy, Top. Organomet.
Chem. 2011, 34, 169–208; g) W.-B. Liu, J.-B. Xia, S.-L.
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0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7.26–7.07 (m,
4H), 6.40 (s, 1H), 6.06 (ddd, J=6.6, 10.2, 17.4 Hz, 1H), 5.62
(s, 1H), 5.21 (d, J=10.2 Hz, 1H), 4.94 (d, J=17.4 Hz, 1H),
4.63 (d, J=6.6 Hz, 1H), 3.70 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=166.8, 142.8, 141.8, 138.2, 134.2, 129.6, 128.5,
126.9, 126.8, 126.7, 117.3, 52.0, 49.8; IR (film): vmax =2951,
1724, 1594, 1436, 1252, 1139, 785 cmÀ1; EI-MS: m/z (rel.
int.)=236 (M+, 24), 201 (28), 177 (20), 141 (100), 125 (52);
HR-MS (EI): m/z=236.0603, calcd. for C13H13O2Cl [M]+:
236.0604.
5j, colorless oil, yield: 83%, b/l: 95/5, ee: 96% [Daicel
CHIRALCEL OD-H (0.46 cmꢂ25 cm); n-hexane/2-propa-
nol=80/20; flow rate=0.5 mL·minÀ1
;
detection wave-
length=214 nm]: tR =5.66 (major), 7.18 (minor) min, [a]2D0:
1
+67.5 (c 0.5, CHCl3). H NMR (300 MHz, CDCl3): d=7,19
(d, J=4.2 Hz, 1H), 6.96–6.93 (m, 1H), 6.82 (m, 1H), , 6.39
(s, 1H), 6.07 (ddd, J=6.9, 9.9, 16.8 Hz, 1H), 5.64 (s, 1H),
5.21 (d, J=9.9 Hz, 1H), 5.08 (d, J=16.8 Hz, 1H), 4.92 (d,
J=6.9 Hz, 1H), 3.74 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=166.8, 144.3, 142.2, 138.3, 126.8, 126.5, 125.3, 124.3, 116.7,
52.0, 45.1; IR (film): vmax =3106, 2951, 1724, 1628, 1436,
1250, 1138, 699 cmÀ1; EI-MS: m/z (rel. int.)=208 (M+, 58),
176 (38), 147 (100), 123 (32), 115 (32); HR-MS (EI): m/z=
208.0562, calcd. for C11H12O2S [M]+: 208.0558.
5k, colorless oil, yield: 77%, b/l: 75/25, [a]2D0: À24.5 (c 0.5,
CHCl3). 13C NMR (75 MHz, CDCl3): d=167.6, 167.5, 143.4,
140.3, 133.1, 126.3, 125.0, 124.1, 115.1, 51.8, 44.6, 35.8, 34.7,
34.6, 22.5, 20.4, 13.9, 13.66; IR (film): vmax =2957, 2931,
2873, 1724, 1437, 1250, 1150 cmÀ1; EI-MS: m/z (rel. int.)=
168 (M+, 16), 125 (100), 109 (44), 93 (45), 79 (88), 67 (52);
HR-MS (EI): m/z=168.1156, calcd. for C10H16O2 [M]+:
168.1150.
Procedure for Synthesis of g-Lactone (R)-6
The product 4a (38.0 mg, 0.2 mmol) was dissolved in MeOH
(2 mL), and then cooled to À788C. Into this mixture O3 was
bubbled until the color of the system changed to blue, then
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FULL PAPERS
Iridium-Catalyzed Enantioselective Allylic Alkylation of
Methyl 2-(4-nitrophenylsulfonyl)acetate and Subsequent
Transformations
9
Adv. Synth. Catal. 2012, 354, 1 – 9
Qing-Long Xu, Li-Xin Dai, Shu-Li You*
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These are not the final page numbers!