Rhodium-catalyzed asymmetric cycloisomerization of 1,6-ene-ynamides

Article abstract of DOI:10.1002/adsc.201300148

The rhodium-catalyzed asymmetric cycloisomerization of heteroatom-bridged 1,6-ene-ynamides proceeded to give high yields of functionalized 3-aza- and oxabicyclo[4.1.0]heptene derivatives with high enantioselectivity, which was achieved by use of a rhodium/chiral diene catalyst. The 1,6-ene-ynamides substituted with 2-oxazolidinone and 2-azetidinone moieties at the alkyne terminus were found to display high reactivity towards the rhodium/chiral diene catalyst, where the chelate coordination of the alkyne moiety and the carbonyl oxygen of the ene-ynamides might be responsible for the high catalytic activity. Copyright

Full text of DOI:10.1002/adsc.201300148

FULL PAPERS
DOI: 10.1002/adsc.201300148
Rhodium-Catalyzed Asymmetric Cycloisomerization of 1,6-Ene-
ynamides
Takahiro Nishimura,a,* Yuka Takiguchi,a Yuko Maeda,a and Tamio Hayashib,c,*
a
Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan
Fax : (+81)-75-753-3988; e-mail: tnishi@kuchem.kyoto-u.ac.jp
Institute of Materials Research and Engineering, A*STAR, 3 Research Link, Singapore 117602
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543
b
c
Fax : (+65)-6872-0785; e-mail: tamioh@imre.a-star.edu.sg
Received: February 13, 2013; Published online: April 30, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300148.
Abstract: The rhodium-catalyzed asymmetric cyclo- display high reactivity towards the rhodium/chiral
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
high enantioselectivity, which was achieved by use of activity.
a rhodium/chiral diene catalyst. The 1,6-ene-yna-
mides substituted with 2-oxazolidinone and 2-azetidi- Keywords: asymmetric synthesis; chiral diene; cycloi-
none moieties at the alkyne terminus were found to somerization; ene-ynamides; rhodium
Introduction
where it is proposed that a 6-endo cyclization via the
electrophilic activation of an alkyne moiety by p-
Since the initial development of the cycloisomeriza- acidic metals, such as Pt,[4] Au,[5] Rh,[6] and Ir,[7,8]
tion of 1,n-enynes through palladium catalysis by forms a metal carbenoid or a metal-stabilized cationic
Trost and co-workers,[1] the transition metal-catalyzed species, and the following 1,2-hydrogen shift gives a bi-
cycloisomerization has been one of the most powerful cyclic compound (Scheme 1).
methods for the preparation of complicated cyclic
An asymmetric variant of this type of reaction is
compounds in a single step.[2] Considerable efforts valuable[3] because the chiral bicyclic compounds con-
have also been made to achieve the enantioselective taining heteroatoms have potential biological activi-
cycloisomerization and this has been realized in the ties.[9] In 2005, Shibata and co-workers reported the
last decade.[3] Of several cycloisomerization reactions first asymmetric cycloisomerization of nitrogen-
leading to cyclic compounds, a useful method for the bridged 1,6-enynes catalyzed by an iridium/bisphos-
synthesis of bicycloACTHNUTRGNEUNG
[4.1.0]heptene derivatives is the phine complex under CO.[10] Fensterbank and co-
cycloisomerization of heteroatom-bridged 1,6-enynes, workers reported that iridium complexes with chiral
Scheme 1. Cycloisomerization of heteroatom-bridged 1,6-enynes.
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Rhodium-Catalyzed Asymmetric Cycloisomerization of 1,6-Ene-ynamides
Scheme 2. Rhodium-catalyzed asymmetric cycloisomerization of 1,6-enynes.
counterions effectively catalyzed the same type of the
ACHTUNGTRENaNGNU mide took place in the presence of a rhodium/chiral
reaction.[11] Chiral bisphosphine/NHC- and mono- diene[21] catalyst (Table 1). Thus, the reaction of ene-
phosphine/cyclometalated NHC-platinum complexes ynamide 1a in the presence of {RhClACTHUNRTGNE[GNU (S,S)-Fc-
[22]
have been developed by Marinetti and co-workers.[12] tfb*]}2 (Fc=ferrocenyl, tfb=tetrafluorobenzobarre-
Michelet and co-workers reported that the asymmet- lene;[23] 2 mol% of Rh) in 1,2-dichloroethane at 308C
ric cycloisomerization with high enantioselectivity is for 18 h gave 95% yield of the cycloisomerization
catalyzed by chiral gold/bisphosphine complexes.[13] product 2a, whose ee was 97% (entry 1). In the pres-
The gold-catalyzed asymmetric cycloisomerization has ent reaction, the addition of NaBArF [ArF =3,5-bis-
4
also been applied to the synthesis of antidepressive
ACHTUNGTREN(NGNU trifluoromethyl)phenyl], which is essential for the
drug candidates by Elitzin[14] and Fꢁrstner,[15] inde- formation of the cationic rhodium species in our pre-
pendently.[16] In this context, we recently reported vious studies,[17] was not required: both reactions with
that rhodium(I) complexes coordinated with a chiral and without NaBArF gave the same yield (75%) of
4
diene and a phosphorus moiety are good catalysts for 2a for 3 h (entries 2 and 3). Of several chiral diene li-
the asymmetric cycloisomerization of nitrogen- and gands (Fc-, Ph-, Bn-tfb*, and L1,[21f] entries 1, 4–6)
oxygen-bridged 1,6-enynes (Scheme 2),[17] where the and a bisphosphine ligand [(R)-binap; entry 7], Fc-
active cationic rhodium species such as A and B were tfb* was found to be the best ligand displaying high
generated. Thus, the designed cationic rhodium(I) cat- catalytic activity and enantioselectivity.
alysts have
vacant site for the electrophilic activation of the alkyne moiety and carbonyl oxygen of the ene-yn-
alkyne moiety, which is created by the ligand coordi- amides is essential for the high catalytic activity. Thus,
a
stereochemically controlled single
It is likely that the chelate coordination of the
AHCTUNGTRENNUNG
nation (Type I).[18] We next focused on an alternative the reaction of 1,6-enyne 3 substituted with a methyl
concept for the formation of such rhodium species, group at the alkyne terminus did not take place at all
which involves the use of a chelate coordination of under the same reaction conditions (Scheme 3). The
the alkyne moiety and a functional group on the ene- 1,6-enyne 3 was a good substrate giving the corre-
yne compound (Type II).[19] Here we report the asym- sponding cycloisomerization product in high yield
metric cycloisomerization of nitrogen- and oxygen- with high enantioselectivity by use of the Type I cata-
bridged 1,6-ene-ynamides[20] bearing an amide moiety lyst (Scheme 2) in our previous studies.[17] The reac-
at the alkyne terminus to give bicyclo
ACHTUNGERTN[NUNG 4.1.0]heptene tion of oxygen-bridged ene-ynamide 4 bearing a tosy-
derivatives with high enantioselectivity, which was re- lamide group also did not proceed, despite the fact
alized by use of a rhodium/chiral diene catalyst.
that oxygen-bridged 1,6-ene-ynamides substituted
with 2-oxazolidinone at the alkyne terminus are good
substrates to give high yields of the cycloisomeriza-
tion products (vide infra).
Results and Discussion
The relative and absolute configuration of 2a ob-
Based on the concept described in Scheme 2, we pre- tained with (S,S)-Fc-tfb* was determined to be
pared a nitrogen-bridged 1,6-ene-ynamide substituted (1S,6R,7S) by X-ray crystallographic analysis
with 2-oxazolidinone at the alkyne terminus, and it (Figure 1).[24]
was found that the cycloisomerization of this ene-yn-
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Table 1. Rhodium-catalyzed asymmetric cycloisomerization of 1,6-ene-ynamide 1a.[a]
Entry
Ligand
Time [h]
Yield [%][b]
ee [%][c]
97
1
A
N
N
N
18
3
3
18
18
18
18
95[d]
75
[e]
2
–
–
3[f]
4
75
[e]
92[d]
36
96
66
85
90
5
6
7
ACHTUNGTRENNUNG
(R)-L1
(R)-binap
83
7
[a]
Reaction conditions: 1a (0.10 mmol), [RhCl(L*)]2 (2 mol% of Rh) in 1,2-dichloroethane (0.5 mL) at 308C for 18 h.
Determined by H NMR.
Determined by HPLC analysis with a chiral stationary phase column: Chiralpak IA.
Isolated yield.
[b]
[c]
[d]
[e]
[f]
1
Not determined.
Performed with NaBArF (4 mol%).
4
Scheme 3. Reactivity of 1,6-enynes.
Scheme 4 summarizes the results obtained for the
cycloisomerization of several ene-ynamides. Asym-
metric cycloisomerization can be applied to the ene-
ynamides bearing not only p-toluenesulfonyl (Ts: 1a)
on the nitrogen atom, but also 2-nitrobenzenesulfonyl
(o-Ns: 1b), tert-butoxycarbonyl (Boc: 1c), and benzyl-
Figure 1. ORTEP illustration of 2a (a solvent molecule is
omitted for clarity).
ACHTUNGTRENNUNGoxycarbonyl (Cbz: 1d) to give the corresponding bicy-
clic compounds 2a–2d in high yields, the enantioselec-
tivity ranging between 93 and 97% ee. The reaction of
ene-ynamides substituted with 2-methoxyphenyl (1e)
and propyl (1f) on the alkene moiety (R2) and phenyl ene-ynamides 1i–1m to give the corresponding oxabi-
(1g) on R1 proceeded to give the corresponding bicy- cyclic compounds 2i–2m with 85–95% ee.
clic compounds 2e–2g in high yields with 82, 65, and
The cycloisomerization product 2c obtained here
90% ee, respectively. The reaction of ene-ynamide 1h with 94% ee was readily converted into a 3-
AHCTUNGTRENNUNG
derived from 2-azetidinone gave the corresponding azabicycloACTHUNRTGNE[GNU 4.1.0]heptane derivative, which is one of
bicyclic compound 2h in 92% with 85% ee. The same the basic structures displaying biological activity[9]
type of reaction was observed for oxygen-bridged (Scheme 5). Thus, treatment of 2c with triethylsilane
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Rhodium-Catalyzed Asymmetric Cycloisomerization of 1,6-Ene-ynamides
Scheme 6. Proposed stereochemical model.
and trifluoroacetic acid gave bicyclic amine 6 in 97%
yield without loss of its enantiomeric purity (94% ee),
where the reduction of the alkene moiety and remov-
al of the Boc group on nitrogen were carried out at
once.
Provided that the present rhodium-catalyzed cyclo-
AHCTUNGTREGUNiNN somerization proceeds via a rhodium carbenoid as
previously proposed for the platinum-catalyzed reac-
tion,[2,4a,25] the enantioselectivity observed in the pres-
ent catalytic system can be rationalized by using a ste-
reochemical model as shown in Scheme 6. The pro-
posed cationic rhodium species C is coordinated with
an alkyne moiety and a carbonyl oxygen of ene-yn-
AHCTUNGTREGaNNUN mide 1a. The favorable conformation of the coordi-
nated ene-ynamide is illustrated as a C-1 structure,
where an N-tosyl group is placed at a less shielded
site avoiding the steric repulsion (C-2) between the
N-tosyl group and a ferrocenyl group of the ligand
(S,S)-Fc-tfb*. The 6-endo-dig cyclization from C-
1 gives the rhodium-carbenoid D-1, which leads to
(1S,6R,7S)-2a.
Scheme 4. Rhodium-catalyzed asymmetric cycloisomeriza-
tion of 1,6-ene-ynamides 1. Reaction conditions:
1 (0.20 mmol), [RhClACHTUNTGRNE(NUG (S,S)-Fc-tfb*)]2 (2 mol% of Rh) in 1,2-
dichloroethane (1.0 mL) at 308C. The yields are isolated
yields and the ees were determined by chiral HPLC analysis.
Conclusions
In conclusion, we have developed a rhodium-cata-
lyzed asymmetric cycloisomerization of heteroatom-
bridged 1,6-ene-ynamides giving high yields of func-
tionalized 3-aza- and oxabicycloACHTUNTRGNEUNG[4.1.0]heptene deriva-
tives with high enantioselectivity, which was achieved
by use of a rhodium/chiral diene catalyst. The 1,6-
ene-ynamides substituted with 2-oxazolidinone and 2-
Scheme 5. Transformation of 2c.
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azetidinone at the alkyne terminus were found to dis- General Procedure for Asymmetric Cycloisomer-
play high reactivity toward the rhodium/chiral diene ization of 1,6-Ene-ynamides
catalyst, where the chelate coordination of the alkyne
A mixture of {RhClACHTUNTRGEN[NUG (S,S)-Fc-tfb*]}2 (2.9 mg, 4.0 mmol of
moiety and the carbonyl oxygen of the ene-ynamides
might be responsible for the high catalytic activity.
Rh), 1,6-ene-ynamides 1 (0.20 mmol) in 1,2-dichloroethane
(1.0 mL) was stirred at 308C under N2. The mixture was
passed through a short column of alumina with ethyl acetate
as eluent. After removal of the solvent, the residue was sub-
jected to preparative TLC on silica gel with hexane/ethyl
acetate to give 2.
Experimental Section
3-{(1S,6R,7S)-7-Phenyl-3-tosyl-3-azabicycloACHTUNTRGNEU[GN 4.1.0]hept-4-
General and Materials
en-6-yl}oxazolidin-2-one (2a): The ee was measured by
HPLC (Chiralpak IA column, hexane/CHCl3/2-propanol=
12:4:1, flow 0.7 mLminÀ1, 254 nm): t1 =9.7 min (major), t2 =
18.9 min (minor); [a]D20: À95 (c 1.00, CHCl3) for 97% ee
(1S,6R,7S). 1H NMR (600 MHz, CDCl3): d=2.17 (d, J=
6.8 Hz, 1H), 2.45 (s, 3H), 2.50 (td, J=8.8, 4.1 Hz, 1H), 2.87
(dd, J=6.8, 2.0 Hz, 1H), 3.24 (dd, J=11.5, 2.0 Hz, 1H), 3.40
(q, J=8.8 Hz, 1H), 3.76 (q, J=8.8 Hz, 1H), 4.09 (td, J=8.8,
4.1 Hz, 1H), 4.14 (d, J=11.5 Hz, 1H), 5.42 (d, J=8.2 Hz,
1H), 6.48 (d, J=8.2 Hz, 1H), 6.98 (d, J=6.8 Hz, 2H), 7.19–
7.29 (m, 3H), 7.34 (d, J=8.1 Hz, 2H), 7.68 (d, J=8.1 Hz,
2H); 13C NMR (150 MHz, CDCl3): d=21.5, 31.8, 36.6, 38.2,
39.7, 42.7, 61.9, 109.6, 122.5, 126.9, 127.0, 127.2, 128.3, 130.0,
134.5, 134.7, 144.2, 158.1; HR-MS (ESI): m/z=433.1198,
calcd. for C22H22N2NaO4S (M+Na)+: 433.1192.
All anaerobic and moisture-sensitive manipulations were
carried out with standard Schlenk techniques under predried
nitrogen. NMR spectra were recorded on a JEOL JNM LA-
500 spectrometer (500 MHz for 1H, 125 MHz for 13C) or
a JEOL JNM ECA-600 spectrometer (600 MHz for 1H,
150 MHz for 13C). Chemical shifts are reported in d (ppm)
referenced to the residual peaks of CDCl3 (d=7.26), CD2Cl2
(d=5.33), DMSO-d6 (d=2.49), and CD3OD (d=3.31) for
1H NMR and CDCl3 (d=77.00), CD2Cl2 (d=53.84), DMSO-
d6 (d=39.50), and CD3OD (d=49.00) for 13C NMR. Optical
rotations were measured on a JASCO P-2200 polarimeter.
Flash column chromatography was performed with silica gel
60 N (spherical, neutral) (Cica-Reagent). Alumina (activat-
ed 200) for column chromatography was purchased from
Nacalai Tesque. 1,2-Dichloroethane was distilled over CaH2.
3-{(1S,6R,7S)-3-[(2-Nitrophenyl)sulfonyl]-7-phenyl-3-
azabicycloACTHNUTRGENUG[N 4.1.0]hept-4-en-6-yl}oxazolidin-2-one (2b): The ee
Rhodium complexes, [RhClACHTNUGRTNEUNG
((R,R)-Bn-tfb*)]2,[22] [RhCl-
ACHTUNGTRENNUNG ACHTUNGTRENNUGN
((R,R)-Ph-tfb*)]2,[22] [RhCl((S,S)-Fc-tfb*)]2,[22] [RhCl((R)-
was measured by HPLC (Chiralpak IA column, hexane/
CHCl3/2-propanol=12:4:1, flow 0.50 mLminÀ1): 254 nm, t1 =
24.5 min (major), t2 =44.5 min (minor); [a]2D0: +31 (c 0.51,
CHCl3) for 93% ee (1S,6R,7S). 1H NMR (600 MHz,
CD2Cl2): d=2.32 (d, J=6.8 Hz, 1H), 2.57 (td, J=8.8,
4.1 Hz, 1H), 2.90 (d, J=6.8, 2.4 Hz, 1H), 3.43 (q, J=8.8 Hz,
1H), 3.49 (dd, J=12.2, 2.4 Hz, 1H), 3.79 (q, J=8.8 Hz, 1H),
4.10 (td, J=8.8, 4.1 Hz, 1H), 4.21 (d, J=12.2 Hz, 1H), 5.61
(d, J=8.2 Hz, 1H), 6.51 (d, J=8.2 Hz, 1H), 7.05 (d, J=
7.5 Hz, 2H), 7.20–7.32 (m, 3H), 7.69 (dd, J=7.5, 2.1 Hz,
1H), 7.73–7.82 (m, 2H), 8.01 (dd, J=7.5, 2.0 Hz, 1H);
13C NMR (150 MHz, CD2Cl2): d=32.2, 37.5, 38.5, 40.7, 43.2,
62.5, 111.4, 122.1, 124.8, 127.4, 127.8, 128.7, 131.17, 131.20,
132.6, 134.9, 135.1, 148.4, 158.5; HR-MS (ESI): m/z=
464.0883, calcd. for C21H19N3NaO6S (M+Na)+: 464.0887.
L1)]2,[21f] and [RhCl((R)-binap)]2,[26] were prepared accord-
ing to the reported procedures.
Preparation of 1,6-Ene-ynamides
A typical procedure for 1a is shown below. The other 1,6-
ene-ynamides are described in the Supporting Information.
N-Cinnamyl-4-methyl-N-[3-(2-oxooxazolidin-3-yl)-
prop-2-yn-1-yl]benzenesulfonamide (1a)
To a mixture of CuCl2 (807 mg, 6.0 mmol), Na2CO3 (6.36 g,
60 mmol), 2-oxazolidinone (6.53 g, 75 mmol), and pyridine
(4.85 mL, 60 mmol) in toluene (50 mL) was added N-cin-
namyl-4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide[27]
(4.88 g, 15 mmol) in toluene (100 mL) at 708C over 4 h
under O2 (1 atm).[28] After completion of the addition, the
mixture was stirred at 708C for 1 h. The mixture was filtered
through a pad of celite and concentrated on a rotary evapo-
rator. The residue was subjected to flash column chromatog-
raphy on silica gel with hexane/CHCl3/ethyl acetate (3:2:1)
to give 1a; yield: 4.03 g (9.8 mmol, 65%). 1H NMR
(500 MHz, CDCl3): d=2.43 (s, 3H), 3.61–3.66 (m, 2H), 4.00
(d, J=6.9 Hz, 2H), 4.27 (s, 2H), 4.33–4.38 (m, 2H), 6.06 (dt,
J=15.9, 6.9 Hz, 1H), 6.64 (d, J=15.9 Hz, 1H), 7.22–7.36 (m,
7H), 7.78 (d, J=8.3 Hz, 2H); 13C NMR (125 MHz, CDCl3):
d=21.5, 36.4, 46.4, 48.8, 62.9, 64.7, 75.5, 122.7, 126.5, 127.7,
128.0, 128.5, 129.6, 135.0, 136.1, 136.2, 143.4, 155.8; HR-MS
(ESI): m/z=433.1193, calcd. for C22H22N2NaO4S (M+Na)+:
433.1192.
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
measured by HPLC (Chiralpak IA column, hexane/CHCl3/
2-propanol=12:4:1, flow 0.7 mLminÀ1, 254 nm): t1 =6.5 min
(major), t2 =8.0 min (minor); [a]2D0: +34 (c 1.00, CHCl3) for
1
94% ee (1S,6R,7S). H NMR (600 MHz, DMSO-d6, 608C):
d=1.47 (s, 9H), 2.40 (d, J=6.8 Hz, 1H), 2.70–2.80 (m, 2H),
3.32 (br s, 1H), 3.57 (q, J=8.8 Hz, 1H), 3.85 (q, J=8.8 Hz,
1H), 4.09 (td, J=8.8, 6.1 Hz, 1H), 4.17 (d, J=12.2 Hz, 1H),
5.44 (d, J=8.1 Hz, 1H), 6.57 (d, J=8.1 Hz, 1H), 7.19 (d, J=
7.5 Hz, 2H), 7.22 (t, J=7.5 Hz, 1H), 7.29 (t, J=7.5 Hz, 2H);
13C NMR (150 MHz, DMSO-d6, 608C): d=28.9, 30.3, 38.1,
38.9, 39.5, 43.9, 62.7, 81.7, 108.8, 124.0, 127.3, 128.5, 128.9,
136.6, 153.2, 158.3. HR-MS (ESI): m/z=379.1629, calcd. for
C20H24N2NaO4 (M+Na)+: 379.1628.
A
6-(2-oxooxazolidin-3-yl)-7-phenyl-3-
AHCTUNGTRENNUNG
measured by HPLC (Chiralpak IA column, hexane/CHCl3/
2-propanol=12:4:1, flow 0.5 mLminÀ1, 254 nm): t1 =
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Rhodium-Catalyzed Asymmetric Cycloisomerization of 1,6-Ene-ynamides
12.7 min (major), t2 =15.7 min (minor); [a]2D0: +35 (c 1.03,
CHCl3) for 95% ee (1S,6R,7S). H NMR (600 MHz, DMSO-
1-{(1S,6R,7S)-7-Phenyl-3-tosyl-3-azabicycloACTHNGUTERN[UNG 4.1.0]hept-4-
1
en-6-yl}azetidin-2-one (2h): The ee was measured by HPLC
(Chiralpak IA column, hexane/CHCl3/2-propanol=12:4:1,
flow 0.7 mLminÀ1, 254 nm): t1 =7.6 min (major), t2 =
13.1 min (minor); [a]D20: À48 (c 1.03, CHCl3) for 85% ee
(1S,6R,7S). 1H NMR (600 MHz, CDCl3): d=2.10 (d, J=
6.8 Hz, 1H), 2.17 (td, J=5.8, 2.7 Hz, 1H), 2.44 (s, 3H), 2.52
(ddd, J=15.0, 5.8, 2.7 Hz, 1H), 2.65 (ddd, J=15.0, 5.8,
2.7 Hz, 1H), 3.00 (td, J=5.8, 2.7 Hz, 1H), 3.05 (dd, J=6.8,
2.7 Hz, 1H), 3.21 (dd, J=11.6, 2.7 Hz, 1H), 4.09 (d, J=
11.6 Hz, 1H), 5.43 (d, J=8.2 Hz, 1H), 6.45 (d, J=8.2 Hz,
1H), 6.97 (d, J=6.8 Hz, 2H), 7.18–7.28 (m, 3H), 7.34 (d, J=
7.5 Hz, 2H), 7.67 (d, J=8.2 Hz, 2H); 13C NMR (150 MHz,
CDCl3): d=21.5, 30.1, 36.3, 37.2, 37.5, 38.0, 39.6, 110.4,
121.6, 126.8, 127.0, 127.4, 128.3, 130.0, 134.4, 134.7, 144.2,
d6, 608C): d=2.43 (d, J=7.5 Hz, 1H), 2.73 (td, J=8.9,
6.1 Hz, 1H), 2.81 (br s, 1H), 3.41 (br s, 1H), 3.57 (q, J=
8.9 Hz, 1H), 3.85 (q, J=8.9 Hz, 1H), 4.09 (td, J=8.9,
6.1 Hz, 1H), 4.26 (d, J=12.9 Hz, 1H), 5.19 (d, J=12.2 Hz,
1H), 5.21 (d, J=12.2 Hz, 1H), 5.54 (d, J=8.2 Hz, 1H), 6.63
(d, J=8.2 Hz, 1H), 7.17–7.24 (m, 3H), 7.29 (t, J=7.5 Hz,
2H), 7.34 (t, J=6.8 Hz, 1H), 7.36–7.44 (m, 4H); 13C NMR
(150 MHz, DMSO-d6, 608C): d=29.1, 36.9, 38.0, 38.2, 42.7,
61.6, 66.9, 109.0, 122.3, 126.1, 127.3, 127.4, 127.70, 127.74,
128.2, 135.3, 136.0, 153.0, 157.1; HR-MS (ESI): m/z=
413.1462, calcd. for C23H22N2NaO4 (M+Na)+: 413.1472.
3-{(1S,6R,7S)-7-(2-Methoxyphenyl)-3-tosyl-3-azabicyclo-
ACHTUNGTRENNUNG[4.1.0]hept-4-en-6-yl}oxazolidin-2-one (2e): The ee was mea-
sured by HPLC (Chiralpak IA column, hexane/CHCl3/2-
propanol=12:4:1, flow 0.5 mLminÀ1, 254 nm): t1 =13.6 min
(major), t2 =15.6 min (minor); [a]2D0: À115 (c 1.01, CHCl3)
168.1;
HR-MS
(ESI):
m/z=417.1241,
calcd.
C22H22N2NaO3S (M+Na)+: 417.1243.
3-{(1R,6R,7S)-7-Phenyl-3-oxabicycloACHTUNGTERN[NUNG 4.1.0]hept-4-en-6-
for
1
for 82% ee (1S,6R,7S). H NMR (600 MHz, CDCl3): d=2.41
yl}-oxazolidin-2-one (2i): The ee was measured by HPLC
(Chiralcel OD-H column, hexane/2-propanol=4:1, flow
0.5 mLminÀ1, 254 nm): t1 =18.3 min (minor), t2 =19.4 min
(major); [a]2D0: À8 (c 1.03, CHCl3) for 84% ee (1R,6R,7S);
1H NMR (600 MHz, CDCl3): d=2.57–2.62 (m, 1H), 2.61 (d,
J=6.8 Hz, 1H), 2.81 (d, J=6.8 Hz, 1H), 3.46 (q, J=8.8 Hz,
1H), 3.81 (q, J=8.8 Hz, 1H), 4.07 (d, J=10.9 Hz, 1H), 4.12
(td, J=8.8, 4.1 Hz, 1H), 4.31 (d, J=10.9 Hz, 1H), 5.33 (d,
J=6.1 Hz, 1H), 6.27 (d, J=6.1 Hz, 1H), 7.17 (d, J=7.5 Hz,
2H), 7.23 (t, J=7.5 Hz, 1H), 7.29 (t, J=7.5 Hz, 2H);
13C NMR (150 MHz, CDCl3): d=30.7, 36.6, 37.1, 42.8, 60.8,
61.9, 104.5, 126.8, 127.3, 128.3, 135.4, 142.3, 158.2; HR-MS
(ESI): m/z=280.0943, calcd. for C15H15NNaO3 (M+Na)+:
280.0944.
(s, 3H), 2.54 (td, J=8.9, 4.1 Hz, 1H), 2.71 (d, J=7.5 Hz,
1H), 2.90 (dd, J=7.5, 2.4 Hz, 1H), 3.21 (dd, J=10.9, 2.4 Hz,
1H), 3.42 (q, J=8.9 Hz, 1H), 3.66 (q, J=8.9 Hz, 1H), 3.81
(s, 3H), 4.05 (td, J=8.9, 4.1 Hz, 1H), 4.11 (d, J=10.9 Hz,
1H), 5.41 (d, J=8.9 Hz, 1H), 6.50 (d, J=8.9 Hz, 1H), 6.82
(d, J=8.1 Hz, 1H), 6.84–6.89 (m, 2H), 7.17–7.23 (m, 1H),
7.31 (d, J=8.2 Hz, 2H), 7.67 (d, J=8.2 Hz, 2H); 13C NMR
(150 MHz, CDCl3): d=21.4, 30.0, 30.5, 37.5, 39.9, 42.2, 55.3,
61.8, 109.3, 109.9, 120.1, 122.2, 123.0, 126.4, 127.0, 128.0,
129.8, 134.4, 144.0, 158.1, 158.6; HR-MS (ESI): m/z=
463.1297, calcd. for C23H24N2NaO5S (M+Na)+: 463.1298.
3-{(1S,6R,7R)-7-Propyl-3-tosyl-3-azabicycloACHTUNTRGNEU[GN 4.1.0]hept-4-
en-6-yl}oxazolidin-2-one (2f): The ee was measured by
HPLC (Chiralpak AD-H column, hexane/2-propanol=4:1,
flow 0.7 mLminÀ1, 254 nm): t1 =21.0 min (minor), t2 =
22.3 min (major); [a]D20: +74 (c 1.01, CHCl3) for 65% ee
(1S,6R,7R). 1H NMR (600 MHz, CDCl3): d=0.81 (t, J=
7.5 Hz, 3H), 0.82–0.89 (m, 1H), 0.91–1.11 (m, 1H), 1.20–
1.31 (m, 2H), 1.61–1.70 (m, 2H), 2.42 (s, 3H), 3.12 (dd, J=
11.5, 2.0 Hz, 1H), 3.51 (q, J=8.1 Hz, 1H), 3.57 (q, J=
8.1 Hz, 1H), 3.97 (d, J=11.5 Hz, 1H), 4.22–4.33 (m, 2H),
5.38 (d, J=8.1 Hz, 1H), 6.40 (d, J=8.1 Hz, 1H), 7.31 (d, J=
8.2 Hz, 2H), 7.63 (d, J=8.2 Hz, 2H); 13C NMR (150 MHz,
CDCl3): d=13.9, 21.6, 22.2, 30.1, 32.1, 33.7, 35.2, 40.0, 44.4,
62.0, 110.9, 122.1, 127.0, 130.0, 134.9, 144.1, 158.4; HR-MS
(ESI): m/z=399.1350, calcd. for C19H24N2NaO4S (M+Na)+:
399.1349.
3-{(1R,6R,7S)-7-(o-Tolyl)-3-oxabicycloACTHNUTRGNEUGN[4.1.0]hept-4-en-6-
yl}oxazolidin-2-one (2j): The ee was measured by HPLC
(Chiralpak AD-H column, hexane/2-propanol=4:1, flow
0.5 mLminÀ1, 254 nm): t1 =15.2 min (major), t2 =16.9 min
(minor); [a]2D0: +95 (c 1.00, CHCl3) for 87% ee (1R,6R,7S).
1H NMR (600 MHz, CDCl3): d=2.41 (s, 3H), 2.55 (td, J=
8.9, 4.5 Hz, 1H), 2.63 (d, J=7.2 Hz, 1H), 2.90 (d, J=7.2 Hz,
1H), 3.44 (q, J=8.9 Hz, 1H), 3.69 (q, J=8.9 Hz, 1H), 4.06
(td, J=8.9, 4.5 Hz, 1H), 4.10 (d, J=10.6 Hz, 1H), 4.30 (d,
J=10.6 Hz, 1H), 5.39 (d, J=6.1 Hz, 1H), 6.29 (d, J=6.1 Hz,
1H), 6.95 (d, J=6.1 Hz, 1H), 7.09–7.19 (m, 3H); 13C NMR
(150 MHz, CDCl3): d=20.1, 29.3, 34.1, 36.6, 42.1, 61.0, 61.7,
104.7, 125.2, 125.8, 126.8, 129.8, 133.2, 138.0, 142.2, 158.3;
HR-MS (ESI): m/z=294.1101, calcd. for C16H17NNaO3 (M+
Na)+: 294.1101.
3-{(1R,6S)-1-Phenyl-3-tosyl-3-azabicycloACHTNUTRGNEUNG[4.1.0]hept-4-en-
6-yl}oxazolidin-2-one (2g): The ee was measured by HPLC
(Chiralpak IB+IA column, hexane/CHCl3/EtOH=30:10:1,
flow 0.5 mLminÀ1, 254 nm): t1 =37.1 min (major), t2 =
42.1 min (minor); [a]D20: À113 (c 1.03, CHCl3) for 90% ee
3-{(1R,6R,7S)-7-(m-Tolyl)-3-oxabicycloACTHNGUETRNNU[G 4.1.0]hept-4-en-6-
yl}oxazolidin-2-one (2k): The ee was measured by HPLC
(Chiralpak AD-H column, hexane/2-propanol=4:1, flow
0.5 mLminÀ1, 254 nm): t1 =16.4 min (major), t2 =20.4 min
(minor)]; [a]2D0: À8 (c 1.02, CHCl3) for 94% ee (1R,6R,7S).
1H NMR (600 MHz, CDCl3): d=2.32 (s, 3H), 2.57 (d, J=
6.8 Hz, 1H), 2.63 (td, J=8.8, 4.1 Hz, 1H), 2.79 (dd, J=6.8,
1.4 Hz, 1H), 3.44 (q, J=8.8 Hz, 1H), 3.80 (q, J=8.8 Hz,
1H), 4.06 (dd, J=10.2, 2.0 Hz, 1H), 4.13 (td, J=8.8, 4.1 Hz,
1H), 4.29 (dd, J=10.2, 1.4 Hz, 1H), 5.32 (dd, J=6.1, 1.4 Hz,
1H), 6.26 (d, J=6.1 Hz, 1H), 6.94 (d, J=7.5 Hz, 1H), 6.99
(s, 1H), 7.04 (d, J=7.5 Hz, 1H), 7.17 (t, J=7.5 Hz, 1H);
13C NMR (150 MHz, CDCl3): d=21.3, 30.7, 36.5, 36.9, 42.8,
60.8, 61.9, 104.6, 124.1, 127.5, 128.2, 128.3, 135.3, 137.9,
1
(1R,6S). H NMR (600 MHz, CDCl3): d=1.55 (d, J=6.1 Hz,
1H), 1.92 (d, J=6.1 Hz, 1H), 2.47 (s, 3H), 3.13 (q, J=
8.9 Hz, 1H), 3.21 (q, J=8.9 Hz, 1H), 3.37 (d, J=11.5 Hz,
1H), 3.86–3.96 (m, 2H), 3.97 (d, J=11.5 Hz, 1H), 5.47 (d,
J=8.5 Hz, 1H), 6.49 (d, J=8.5 Hz, 1H), 7.25–7.40 (m, 7H),
7.64 (d, J=8.1 Hz, 2H); 13C NMR (150 MHz, CDCl3): d=
21.5, 22.7, 38.4, 41.6, 44.7, 47.0, 61.7, 113.2, 123.2, 127.0,
127.9, 128.6, 128.8, 130.0, 134.7, 135.8, 144.2, 158.0; HR-MS
(ESI): m/z=433.1191, calcd. for C22H22N2NaO4S (M+Na)+:
433.1192.
Adv. Synth. Catal. 2013, 355, 1374 – 1382
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1379

Takahiro Nishimura et al.
FULL PAPERS
142.1, 158.2; HR-MS (ESI): m/z=294.1101, calcd. for
C16H17NNaO3 (M+Na)+: 294.1101.
3-{(1R,6R,7S)-7-(p-Tolyl)-3-oxabicycloACTHNUTRGNEUGN[4.1.0]hept-4-en-6-
3-{(1S,6R,7S)-7-Phenyl-3-tosyl-3-azabicycloACTHNUGRTNEUNG[4.1.0]-
heptan-6-yl}oxazolidin-2-one (s13)
This compound was prepared from 6 and tosyl chloride in
the presence of triethylamine. The ee was measured by
HPLC (Chiralpak IA column, hexane/CHCl3/2-propanol=
15/5/1, flow 0.7 mLminÀ1, 254 nm): t1 =8.8 min (major), t2 =
17.5 min (minor); [a]D20: +42 (c 0.90, CHCl3) for 94% ee
yl}oxazolidin-2-one (2l): The ee was measured by HPLC
(Chiralcel OD-H columnꢂ2, hexane/2-propanol=4:1, flow
0.6 mLminÀ1, 254 nm): t1 =28.3 min (minor), t2 =30.0 min
(major); [a]2D0: +1 (c 1.01, CHCl3) for 95% ee (1R,6R,7S).
1H NMR (600 MHz, CDCl3): d=2.32 (s, 3H), 2.57 (d, J=
6.8 Hz, 1H), 2.65 (td, J=8.8, 4.1 Hz, 1H), 2.76 (d, J=
6.8 Hz, 1H), 3.35 (q, J=8.8 Hz, 1H), 3.83 (q, J=8.8 Hz,
1H), 4.06 (dd, J=10.2, 2.0 Hz, 1H), 4.12 (td, J=8.8, 4.1 Hz,
1H), 4.30 (dd, J=10.2, 1.4 Hz, 1H), 5.33 (dd, J=6.1, 1.4 Hz,
1H), 6.26 (d, J=6.1 Hz, 1H), 7.05 (d, J=8.2 Hz, 2H), 7.10
(d, J=8.2 Hz, 2H); 13C NMR (150 MHz, CDCl3): d=21.0,
30.6, 36.3, 36.8, 42.8, 60.8, 61.9, 104.6, 127.2, 129.0, 132.2,
136.4, 142.1, 158.2; HR-MS (ESI): m/z=294.1103, calcd. for
C16H17NNaO3 (M+Na)+: 294.1101.
1
(1S,6R,7S). H NMR (600 MHz, CDCl3): d=2.00 (ddd, J=
14.3, 4.8, 2.0 Hz, 1H), 2.26–2.37 (m, 3H), 2.41–2.50 (m, 2H),
2.45 (s, 3H), 3.03 (dd, J=11.6, 3.4 Hz, 1H), 3.28 (q, J=
8.9 Hz, 1H), 3.57–3.66 (m, 1H), 3.74 (q, J=8.9 Hz, 1H),
3.92 (d, J=11.6 Hz, 1H), 4.07 (td, J=8.9, 3.0 Hz, 1H), 7.13
(d, J=6.8 Hz, 2H), 7.20–7.24 (m, 1H), 7.25–7.30 (m, 2H),
7.33 (d, J=8.1 Hz, 2H), 7.63 (d, J=8.1 Hz, 2H); 13C NMR
(CDCl3): d=21.5, 24.8, 29.8, 32.8, 38.4, 42.6, 43.4, 43.9, 62.1,
126.7, 127.2, 127.5, 128.3, 129.8, 133.1, 135.8, 143.8, 158.6;
HR-MS (ESI): m/z=435.1344, calcd. for C22H24N2NaO4S
(M+Na)+: 435.1349.
3-{(1R,6R,7S)-7-(2-Methoxyphenyl)-3-oxabicycloACTHNUGTRNEUNG[4.1.0]-
hept-4-en-6-yl}oxazolidin-2-one (2m): The ee was measured
by HPLC (Chiralpak AD-H column ꢂ 2, hexane/2-propa-
nol=4/1, flow 0.5 mLminÀ1, 254 nm): t1 =45.3 min (major),
t2 =46.7 min (minor)]; [a]2D0: +61 (c 1.00, CHCl3) for 85% ee
(1R,6R,7S). 1H NMR (600 MHz, CDCl3): d=2.62 (td, J=
8.9, 4.1 Hz, 1H), 2.83 (d, J=7.5 Hz, 1H), 2.90 (d, J=7.5 Hz,
1H), 3.47 (q, J=8.9 Hz, 1H), 3.72 (q, J=8.9 Hz, 1H), 3.86
(s, 3H), 4.06–4.12 (m, 2H), 4.28 (dd, J=10.2, 1.4 Hz, 1H),
5.35 (d, J=6.1 Hz, 1H), 6.27 (d, J=6.1 Hz, 1H), 6.86 (d, J=
8.1 Hz, 1H), 6.89 (dd, J=8.1, 7.5 Hz, 1H), 6.94 (dd, J=7.5,
1.4 Hz, 1H), 7.21 (ddd, J=8.1, 7.5, 1.4 Hz, 1H); 13C NMR
(150 MHz, CDCl3): d=29.6, 30.6, 36.7, 42.5, 55.6, 61.2, 62.0,
104.8, 110.1, 120.4, 123.9, 126.6, 127.9, 142.1, 158.4, 158.9;
HR-MS (ESI): m/z=310.1050, calcd. for C16H17NNaO4 (M+
Na)+: 310.1050.
Acknowledgements
This work has been supported by a Grant-in-Aid for Scientif-
ic Research from the MEXT, Japan and the UBE Founda-
tion.
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din-2-one (s13) derived from 6. [a]2D0: +88 (c 1.24, CHCl3)
for 94% ee (1S,6R,7S). 1H NMR (500 MHz, CD3OD): d=
1.93 (dt, J=14.2, 5.7 Hz, 1H), 2.15–2.25 (m, 2H), 2.31 (d,
J=7.0 Hz, 1H), 2.65–2.80 (m, 3H), 3.06 (d, J=13.3 Hz,
1H), 3.41 (dd, J=13.3, 5.7 Hz, 1H), 3.48 (q, J=8.8 Hz, 1H),
3.82 (q, J=8.8 Hz, 1H), 4.11 (td, J=8.8, 4.9 Hz, 1H), 7.15–
7.30 (m, 3H), 7.28 (t, J=7.4 Hz, 2H); 13C NMR (125 MHz,
CD3OD): d=24.3, 29.1, 34.7, 40.8, 42.4, 44.0, 44.2, 63.7,
127.4, 128.4, 129.2, 138.3, 160.8. HR-MS (ESI): m/z=
281.1260, calcd. for C15H18N2NaO2 (M+Na)+: 281.1260.
1380
asc.wiley-vch.de
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1374 – 1382

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1381

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Adv. Synth. Catal. 2013, 355, 1374 – 1382