Ligand-accelerated asymmetric [1,2]-Stevens rearrangment of sulfur ylides via decomposition of diazomalonates catalyzed by chiral bisoxazoline/copper complex

Article abstract of DOI:10.1002/adsc.200800536

The first example of catalytic asymmetric [1,2]-Stevens rearrangement reaction of 1,3-oxathiolanes with diazomalonates has been developed and up to 90% ee is achieved by the bisoxazoline 4e/ copper(II) triflate [Cu(OTf) ₂] complex.

Full text of DOI:10.1002/adsc.200800536

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DOI: 10.1002/adsc.200800536
Ligand-Accelerated Asymmetric [1,2]-Stevens Rearrangment of
Sulfur Ylides via Decomposition of Diazomalonates Catalyzed by
Chiral Bisoxazoline/Copper Complex
Jian-Ping Qu,a Zheng-Hu Xu,a Jian Zhou,a Chun-Li Cao,a Xiu-Li Sun,a
Li-Xin Dai,a and Yong Tanga,*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 354 Fenglin Lu, Shanghai 200032, Peopleꢀs Republic of China
Fax : +(86)-21-6416-6128; e-mail: tangy@mail.sioc.ac.cn
Received: August 27, 2008; Revised: November 12, 2008; Published online: February 4, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200800536.
Abstract: The first example of catalytic asymmetric
[1,2]-Stevens rearrangement reaction of 1,3-oxathio-
lanes with diazomalonates has been developed and
up to 90% ee is achieved by the bisoxazoline 4e/
1,3-oxathiolanes. Herein, we wish to report the results
in detail.
Huang et al. found that Cu(I)-mediated decomposi-
tion of ethyl diazomalonate in the presence of dibutyl
telluride could generate the corresponding telluroni-
um ylide, which reacted with aldehydes to give alkyli-
denemalonates.[9] Using sulfide instead of telluride,
we envisaged that it would be possible to form a
chiral sulfur ylide by the reaction of diazomalonate
with a sulfide in the presence of a chiral ligand/Cu(I),
followed by the Stevens rearrangement to furnish op-
tically active sulfur compounds. Initial attempts, by
copper(II) triflate [CuACHTNUTRGNEUNG(OTf)2] complex.
Keywords: asymmetric catalysis; bisoxazolines; Ste-
vens rearrangement; ylides
The asymmetric rearrangement reactions[1] of sulfur employing CuOTf as a catalyst in the absence of
ylides[2] are one of the powerful tools for the prepara- ligand and 2-(4-chlorophenyl)-1,3-oxathiolane as a
tion of optically active sulfur compounds and are very substrate, failed to give the desired product even
useful in organic synthesis. Although the enantioselec- when the reaction temperature was raised to 408C
tive [2,3]-sigmatropic rearrangements of sulfur (entry 1, Table 1). Using 15 mol% of CuOTf in com-
ylides[3] and [1,2]-Stevens reactions of oxygen ylides[4] bination of 10 mol% of bisoxazoline,[10] however, we
have been intensively studied, asymmetric [1,2]-Ste- were pleased to find that the [1,2]-Stevens rearrange-
vens rearrangements of sulfur ylides have seldom ment proceeded smoothly to afford the desired prod-
been explored. To obtain the key intermediate for the uct 3 in good yield with 52% ee (entry 2, Table 1).
total synthesis of showdomycin, Kametani developed This result suggested that the ligand accelerates the
a substrate-controlled asymmetric [1,2]-Stevens rear- reaction and encouraged us to optimize the ligands to
rangment reaction of sulfides with diazomalonate in further improve the yield and selectivity.
1987.[4b] Aggarwal and his co-workers also observed
Recently, sidearmed bisoxazolines[11] have already
the Stevens rearrangement product during their study proved to be excellent ligands in metal-catalyzed Frie-
on the asymmetric sulfur ylide epoxidation reaction.[5] del–Crafts,[12] Kinugasa,[13] Diels–Alder,[14] cyclopropa-
To the best of our knowledge, there is no report on a nation,[15] 1,3-dipolar cycloaddition,[16] and asymmetric
catalytic asymmetric [1,2]-Stevens rearragement reac- allylic substitution and oxidation.[17] Compared with
tion of sulfur ylides. Very recently, we explored side- the parental bisoxazolines, in some cases, these side-
armed bisoxazoline/CuACHTUNRGTNEUNG(OTf)2 as a catalyst in the armed bisoxazolines exhibited better enantiofacial
asymmetric [1,2]-Stevens reaction[6] of 1,3-oxathio- control, higher reactivity, and better tolerance to im-
lane[7] with diazomalonate[8] and up to 90% ee was purities so that reactions could be run in an air atmos-
achieved. This provides the first example of a catalytic phere. Thus, we evaluated various sidearmed bisoxa-
asymmetric [1,2]-Stevens rearrangement reaction of zolines in the aforementioned reaction. The results
were summarized in Table 1. It turned out that the
308
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Ligand-Accelerated Asymmetric [1,2]-Stevens Rearrangment of Sulfur Ylides
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Table 1. Sidearm effects in the reaction [1,2]-Stevens of 1,3-
and enantioselectivity. For example, by employing
ligand 4e, the reaction could finish within 11 h and af-
forded the desired product in almost quantitative
yield with up to 80% ee (entry 6). To further improve
the enantioselectivity, other bisoxazolines 4f–4i with
substituted phenyl groups were designed and tested
(entries 7–10). In these cases, unfortunately, slightly
diminished ee values were observed. We also checked
the effect of bisoxazolines 5 with two phenyl groups
as sidearms, but it turned out to be detrimental
(entry 11). Two commercially available bisoxazolines
6 and 7 were also examined in this reaction. Bisoxazo-
line 6 afforded excellent yield but poor enantioselec-
tivity. 2,6-Bis[(S)-4,5-dihydro-4-isopropyloxazol-2-yl]-
pyridine (PYBOX) did not promote the reaction at
all.
oxathiolane with diazomalonate.[a]
We next screened solvents using bisoxazoline 4e.
As shown in Table 2, diethyl ether, toluene and THF
all gave moderate yields and enantioselectivities.
1,1,2,2-Tetrachloroethane (TTCE) afforded the high-
est ee, but the yield was 26% even if the reaction time
was prolonged to 96 h (entry 5). Although raising
temperature to 508C increased yield, the ee decreased
slightly (entry 6). Of the solvents examined, dichloro-
methane (DCM) was the optimal (entries 1–6). Vary-
ing the ratio of CuOTf and chiral ligand from 1.50/1.0
to 1.20/1.0, the yield was decreased from 99% to 79%
albeit with no loss of enantiomeric excess (entries 1
and 7, Table 2).
Entry
Ligand
Time [h]
Yield[b] [%]
ee[c] [%]
1
2
3
4
5
6
7
8
–
39
39
39
39
39
11
39
39
39
39
39
39
39
0
–
52
0
4a
4b
4c
4d
4e
4f
4g
4h
4i
5
65
24
44
40
99
87
99
44
55
67
99
0
80
82
80
70
78
79
78
73
6
To further improve the enantioselectivity, the ef-
fects of Lewis acids were also examined. The results
are summarized in Table 3. CuACHTNUGTRNE(UNG OAc)2·H2O, FeCl3,
9
10
11
12
13
6
7
Table 2. Effects of solvents and the ratio of copper salt/4e
–
on the rearrangement.[a]
[a]
Reaction conditions: 1 (37.2 mg, 0.2 mmol), 2a (80.3 mg,
0.4 mmol), CuOTf·(1/2benzene) (7.5 mg, 0.03 mmol),
ligand (0.02 mmol), DCM (2.0 mL).
Isolated yield.
[b]
[c]
Determined by Chiral HPLC.
sidearm significantly influenced both the reactivity
and enantioselectivity in this reaction. Pendant groups
such as an ester group, or an oxazolinyl group obvi-
ously slowed down the reaction and only moderate
yields were obtained (entries 3–5). We speculated that
the diminished yields in the case of bisoxazolines 4b–
d resulted from the attenuated Lewis acidity of the
copper catalyst, probably due to the coordination of
the sidearm that retarded the formation of a metallo-
carbene intermediate. Gratifyingly, however, an oxa-
zoline ring as the sidearm impressively increased the
enantiomeric excess up to 82% ee (entries 4 and 5).
Further studies showed that a simple phenyl group as
a pendant group significantly increased the reactivity
Entry
Cu(I)/4e
Solvent
Yield[b] [%]
ee[c] [%]
1
2
3
4
5
6
7
1.50/1
1.50/1
1.50/1
1.50/1
1.50/1
1.50/1
1.20/1
DCM
Et2O
Toluene
THF
TTCE
TTCE
DCM
99
58
69
83
80
72
72
78
82
79
80
26
91[d]
79
[a]
Reaction conditions: 1 (37.2 mg, 0.2 mmol), 2a (80.3 mg,
0.4 mmol), ligand 4e (6.9 mg, 0.02 mmol), solvent
(2.0 mL), 408C.
Isolated yield.
Determined by Chiral HPLC.
508C.
[b]
[c]
[d]
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309

Jian-Ping Qu et al.
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Table 3. Effects of copper salts on the rearrangement.[a]
Table 4. Reaction of diazomalonates with 1,3-oxathiola-
AHCTUNGTRENNUNG
nes.[a,19]
Entry R1 Substrate
No. R
Product Yield[b,c] ee[c,d]
[%] [%]
Entry
Copper salt
Yield[b] [%]
ee[c] [%]
1
2
3
4
5
6
7
8
9
CuOTf·(1/2benzene)
CuOTf·(1/2toulene)
99
49
99
60
80
90[d]
95
43
30
80
55
36
63
83
83
71
10
3
1
2
3
4
Me 2a
Et 2b
Bn 2c
Bn 2d
3a
3b
3c
3d
94 (85) 78 (78)
80 (73) 83 (80)
97 (98) 88 (86)
CuPF ·
(CH3CN)4
4 A(CH3CN)4
(OTf)2
(OTf)2
(SbF6)2
(BF4)2
(TFA) ·
CuClO ·
G
Cu
Cu
Cu
Cu
Cu
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
90
90 (81)
(85)[e]
G
N
[a]
Reaction conditions: 1 (37.2 mg, 0.2 mmol), 2a (80.3 mg,
0.4 mmol), copper salt (0.03 mmol), ligand 4e (6.9 mg,
0.02 mmol), DCM (2.0 mL).
Isolated yield.
Determined by Chiral HPLC.
5
Bn 2e
3e
95 (84) 83 (80)
98 (91) 89 (86)
[b]
[c]
[d]
6
7
8
Bn 2f
Bn 2g
3f
3g
Reaction was run in air atmosphere.
(90)
(85)
(80)
(52)
Fe
ACHTUNGTRENNUNG(ClO4)3·ACHTUNGTRENNUNG(H2O)9, ZnAHCUTNRTEG(NNGNU ClO4)2·AHCTUGNTRNEN(UNG H2O)6 and CoCAHTUNTGRENU(GN ClO4)2·
Bn 2h
Bn 2i
3h
3i
ACHTUNGTRENNUNG(H2O)6 failed to promote the reaction under the same
reaction conditions. CuOTf·(1/2toluene) was less
enantioselective and less reactive than CuOTf·
(1/2benzene) (entry 2, Table 2). Other Cu(I) salts
with different counter anions, such as CuPF6·
9
66 (90) 23 (38)
[a]
Reaction conditions: 1 (0.2 mmol), 2 (0.4 mmol), Cu-
(OTf)2 (10.9 mg, 0.03 mmol), ligand 4e (6.9 mg,
0.02 mmol), DCM (2.0 mL).
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG(CH3CN)4 and CuClO4·CAHTUNGTREN(NUNG CH3CN)4, worked smoothly
[b]
[c]
Isolated yield.
but gave lower enantioselectivities than CuOTf·(1/
2benzene). In a previous study on the application of
pseudo C3-symmetric trisoxazolines in asymmetric
synthesis,[11–17] we developed the first example of a
Cu(II)-catalyzed asymmetric Kinugasa reaction,[12] in
which Cu(II) was proven to give better ees than the
corresponding Cu(I). Thus, Cu(II) salts were tested.
The data in parenthesis were obtained using ligand 4g
(0.02 mmol).
Determined by chiral HPLC.
[d]
[e]
The absolute configuration of product 3d was determined
to be R by X-ray crystallography.[20]
To our delight, CuACTHNUTRGNE(UNG OTf)2 in combination with bisoxa- nate gave the best result, and 88% ee was obtained.
zoline 4e proved to be more enantioselective and up Substituent R2 on 1,3-oxathiolane has a slight effect
to 83% ee could be achieved. Noticeably, the reaction on the yields and strong effect on the enantioselectivi-
could be carried out in an air atmosphere without loss ties. For instance, when R2 was either an electron-do-
of reactivity and enantioselectivity, which can greatly nating or an electron-withdrawing substituted phenyl
simplify the experimental procedure (entry 6). group, the reactions gave the desired products in high
Cu
ACHTUNGTRENNUNG(BF4)2 and CuACHTUNGTRENU(NG TFA)2·ACUTNGHTR(NNNEUG H2O)2 gave low yields with yields (81–98%, entries 3–8). For enantiofacial selec-
low ees (entries 8 and 9).
tivities, 1,3-oxathiolanes with a benzene ring bearing
On the basis of the systematic study of the effects electron-withdrawing groups such as a halogen and a
of ligands, solvents, and Lewis acids on the reaction, CF3 could furnish the corresponding 1,4-oxathianes
we evaluated the generality of the current reaction by with high ees (entries 3–7). However, an electron-do-
investigating various 1,3-oxathiolanes (2.0 equiva- nating group on the benzene ring decreased the selec-
lents) in CH2Cl2 at 408C in the presence of 4 ꢂ mo- tivity greatly (entry 8). Noticeably, there are two pos-
lecular sieves and 10 mol% of the bisoxazoline sible reactions for substrate 2i: [1,2]-Stevens rear-
4e/CuACHTUNGTRENNUNG(OTf)2 complex. As shown in Table 4, the ester rangement and [2,3]-sigmatropic rearrangement. In
groups of diazomalonates proved to influence the the present conditions, fortunately, only the [1,2]-shift
enantioselectivities (entries 1–3). Compared with product was obtained in good yield with up to 38% ee
methyl and ethyl diazomalonates, benzyl diazomalo- (entry 9). By employing ethyl diazoacteate and ethyl
310
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Ligand-Accelerated Asymmetric [1,2]-Stevens Rearrangment of Sulfur Ylides
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ferred to diazomalonate (62 mg, 0.20 mmol) via a syringe,
followed by addition of 1,3-oxathiolane 2d (98 mg,
0.40 mmol) and MS 4 ꢂ (250 mg). The mixture was further
stirred at 408C. When the reaction was complete (monitored
by TLC), the reaction mixture was filtered through a thin
pad of silica gel (300–400 mesh), washed with CH2Cl2
(50 mL). The filtrate was concentrated under reduced pres-
sure, and the residue was purified by flash chromatography
to afford the product 3d as a colorless oil; yield: 90%; ee
90%. [a]2D0: À43.68 (c 1.00, CDCl3); 1H NMR (300 MHz,
CDCl3): d=7.34–7.23 (m, 10H), 7.14 (d, J=6.9 Hz, 2H),
6.98 (d, J=6.9 Hz, 2H), 5.24 (s, 1H), 5.13–5.00 (m, 3H),
4.87 (d, J=12.6 Hz), 4.34 (dt, J=12.0, 3.3 Hz, 1H), 3.90 (dt,
J=13.2, 12.0 Hz, 1H), 3.53 (td, J=13.2, 3.3 Hz 1H), 2.49 (d,
J=12.9 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=167.25,
166.65, 137.23, 134.54, 134.43, 130.69, 129.86, 128.86, 128.44,
128.40, 128.35, 128.28, 128.12, 128.02, 127.83, 122.29, 81.25,
68.34, 67.78, 67.60, 56.50, 25.91; IR (thin film): n=1731,
1488, 1455, 1242, 1225, 1181, 1100, 1011, 749, 696 cmÀ1; LR-
MS-ESI: m/z=551 ([M+Na]+); HR-MS-ESI: m/z=
549.0348 [M+Na]+, calcd. for C26H23O5BrS+Na: 549.0342.
The ee was determined by HPLC analysis using a Chiralpak
AD-H column (150 mm) with hexane/i-PrOH 95/5 as eluent,
a-phenyldiazoacetate instead of ethyl diazomalonates
the reaction worked well to give the desired products
but the diastereoselectivity was very poor.[18]
A possible mechanism for this asymmetric rear-
rangement is proposed as shown in Scheme 1. The
Scheme 1. Possible mechanism of the rearrangement.
254 nm, 0.7 mLminÀ1,
26.13 min (major).
tR1 =18.96 min (minor), tR2 =
copper complex decomposes diazomalonate and then
reacts with oxathiolane to generate chiral sulfur ylide
8 in which BOX/Cu(I)[21] coordinates to the malonate.
The ylide undergoes a Stevens rearrangement to give
the desired product 3 and regenerate the catalyst. A
clear mechanism must await further investigation.
In summary, we have developed the first example
of catalytic asymmetric [1,2]-Stevens rearrangement
reaction of sulfur ylides. The current reaction can be
Acknowledgements
We are grateful for the financial supported from the National
Natural Science Foundation of China, the Major State Basic
Research Development Program (Grant No. 2006CB806105),
the Chinese Academy of Sciences, and the Science and Tech-
nology Commission of Shanghai Municipality.
run in an air atmosphere when the CuACTHNUTRGENUG(N OTf)2/4e com-
plex is used as the catalyst. Thus, it provides an easy
access to optically active 1,4-oxathianes in high yields
with good to high enantioselectivities under mild con-
ditions. Studies on the further improvement of enan-
tioselectivity and understanding of the mechanism are
in progress in our laboratory.
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General Procedure for the Enantioselective [1,2]-
Stevens Rearrangement (3d as Example)
A mixture of CuACHTUNGTRENNUNG(OTf)2 (10.9 mg, 0.03 mmol, 15 mol%) and
the ligand 4e (6.9 mg, 0.02 mmol, 10 mol%) in CH2Cl2
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Adv. Synth. Catal. 2009, 351, 308 – 312
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Adv. Synth. Catal. 2009, 351, 308 – 312