Asymmetric Baeyer-Villiger oxidation of cyclic ketones using chiral organoselenium catalysts

Article abstract of DOI:10.1246/bcsj.75.2233

Novel optically active diselenides having a chiral oxazoline have been prepared and the structure of one of them is unambiguously determined by X-ray structural analysis. Treatment of a variety of cyclobutanones with 30% H₂O₂ in the presence of a catalytic amount of the optically active diselenides in tetrahydrofuran or 1,4-dioxane at 0 °C-rt affords the corresponding γ-lactones in up to 92% yield with up to 19% ee. The enantioselectivity of the product is not yet satisfactory, but this is the first example of asymmetric Baeyer-Villiger oxidation catalyzed by chiral organoselenium compounds.

Full text of DOI:10.1246/bcsj.75.2233

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 2233–2237 (2002) 2233
e Chemical
ciety of Ja-
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e Chemical
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Asymmetric Baeyer–Villiger Oxidation of Cyclic Ketones Using Chiral
Organoselenium Catalysts
Asymmetric Baeyer–Villiger Oxidation
Y. Miyake et al.
Yoshihiro Miyake, Yoshiaki Nishibayashi, and Sakae Uemura*
02
33
37
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University,
Sakyo-ku, Kyoto 606-8501
SJA8
09-2673
123
(Received May 10, 2002)
Novel optically active diselenides having a chiral oxazoline have been prepared and the structure of one of them is
unambiguously determined by X-ray structural analysis. Treatment of a variety of cyclobutanones with 30% H2O2 in the
presence of a catalytic amount of the optically active diselenides in tetrahydrofuran or 1,4-dioxane at 0 °C–rt affords the
corresponding γ-lactones in up to 92% yield with up to 19% ee. The enantioselectivity of the product is not yet satisfac-
tory, but this is the first example of asymmetric Baeyer–Villiger oxidation catalyzed by chiral organoselenium com-
pounds.
02
02
Baeyer–Villiger oxidation is one of the most valuable meth-
ods for the transformation of ketones into the corresponding
esters.1 Especially, the oxidation of cyclic ketones is widely
used for the synthesis of lactones. In the last decade, transition
metal-catalyzed Baeyer–Villiger oxidation2 using clean oxi-
dants such as molecular oxygen3 and hydrogen peroxide4 has
been developed and studied extensively. In contrast, asymmet-
ric Baeyer–Villiger oxidation has been limited until recently to
Chart 1. Optically active diselenides.
the use of biocatalysts5 such as enzymes obtained from various
microorganisms. However, since the first example of the tran-
sition metal-catalyzed asymmetric Baeyer–Villiger oxidation
chiral 2-phenyl-2-oxazolines in several steps as shown in
of cyclic ketones was reported independently by Bolm et al.6a
Scheme 1. The molecular structure of the diselenide 1c was
and Strukul et al.,7a nonenzymatic asymmetric Baeyer–Villiger
unambiguously clarified by X-ray structural determination, an
oxidation has been intensively studied by several groups.6–8
ORTEP drawing of which is shown in Fig. 1. From the X-ray
Peroxyseleninic acid (RSe(O)O2H), obtained by oxidation
analysis, the distances between the selenium atom and the ni-
of seleninic acid (RSeO2H) with oxidants, is known to be an
trogen atom of 2-oxazoline ring were revealed to be Se1–N1 =
effective oxidant for epoxidation of alkenes9 and Baeyer–Vil-
2.69 Å and Se2–N2 = 2.89 Å, which were shorter than the
liger oxidation of ketones.9c,10 However, no successful report
sum of van der Waals radii of Se and N (3.45 Å).14 This result
on the asymmetric Baeyer–Villiger oxidation using peroxyse-
suggests the existence of Se≥N interaction, as has been report-
leninic acid has appeared so far.11 We have so far developed
ed.12d,15
preparative methods for a variety of optically active organose-
Next, asymmetric Baeyer–Villiger oxidation of 3-phenylcy-
lenium compounds such as selenoxides, selenimides and sele-
clobutanone (2a) with 30% H2O2 aqueous solution was carried
nium ylides and utilized them in several asymmetric reactions
out in tetrahydrofuran (THF) at room temperature in the pres-
where a chiral center on the selenium atom is a key point to ob-
ence of a catalytic amount of chiral diselenides 1 (Eq. 1). Typ-
tain the chiral organic compounds.12 We now report the results
ical results are shown in Table 1. In all cases, the correspond-
of the asymmetric Baeyer–Villiger oxidation of cyclic ketones
ing lactone (3a) was obtained in good yields, but unfortunately
catalyzed by chiral organoselenium compounds in which per-
with low selectivities (Table 1, Entries 1, 2 and 3). Separately,
oxyseleninic acid is an oxidant for the catalytic transformation.
it was confirmed that no reaction proceeded in the absence of
1. The addition of Sc(OTf)3 (0.02 molar amounts to the ke-
tone) as Lewis acid improved the yield of 3a, but no improve-
Results and Discussion
At first, we prepared several optically active diselenides 1
(Chart 1) having a chiral 2-oxazoline, because the correspond-
ing peroxyseleninic acids generated in situ from 1 may be used
for asymmetric Baeyer–Villiger oxidation. Chiral diselenide
1a has been prepared by Wirth and co-workers.13 Novel dise-
lenides (1b and 1c) were prepared from the corresponding
ment of enantioselectivities was observed (Entries 4, 5 and 6).
Interestingly, the addition ofYb(OTf)3 (0.02 molar amounts) to
the reaction system by using 1b slightly improved the enanti-
oselectivity of 3a up to 13% ee (Table 1, Entry 8). On the oth-
er hand, no influence was observed in the reaction using 1a
(Table 1, Entry 7). These results suggest that the coordination

2234 Bull. Chem. Soc. Jpn., 75, No. 10 (2002)
Asymmetric Baeyer–Villiger Oxidation
Scheme 1. Preparation of optically active diselenides.
Table 1. Asymmetric Baeyer–Villiger Oxidation of 3-Phenylcyclobutanone (2a)a)
Entry
Cat.
Lewis Acid
Solvent
Yield/%
Ee/%
1
2
3
4
5
6
7
8
9
10
11
12b)
13c)
1a
1b
1c
1a
1b
1c
1a
1b
1c
1b
1b
1b
1b
—
—
—
THF
THF
THF
THF
THF
THF
THF
THF
THF
66
84
77
100
100
100
88
91
79
92
75
5
6
3
0
4
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
Yb(OTf)3
7
0
13
7
15
10
19
12
1,4-dioxane
1,2-dimethoxyethane
THF
54
31
THF
a) Reaction conditions; 2a (0.50 mmol), cat. (0.0050 mmol), Lewis acid (0.010 mmol),
30% aq H2O2 (75 µL), pH 7.4 phoshate buffer solution (10 µL), solvent (1 mL), at room
temperature for 24 h. b) At 0 °C. c) At −20 °C.
amount to the ketone) andYb(OTf)3 were then investigated un-
der several reaction conditions. Similar results were obtained
in other solvents such as 1,4-dioxane and 1,2-dimethoxyethane
(Table 1, Entries 10 and 11). The best enantioselectivity (19%
ee) was obtained in the oxidation of 2a at 0 °C to give 3a in
54% yield (Table 1, Entry 12).
(1)
Fig. 1. The ORTEP drawing of optically active diselenide
1c. Selected bond lengths, angles, torsion angle (Å, deg,
deg): Se1–Se2 = 2.333(1); C7–N1 = 1.25(1); C22–N2 =
1.22(1) O1–C7–N1 = 119.5(8); O3–C22–N2 = 119.4(10);
C1–Se1–Se2–C17 = −85.7(4).
Treatment of other 3-substituted cyclobutanones 2b and 2c
with H2O2 in the presence of 1b afforded the corresponding
lactones 3 with similar enantioselectivities (Eq. 2). The
Baeyer–Villiger oxidation of tricyclic ketone 46d,16 was also in-
vestigated, the corresponding lactone 5 being obtained in 66%
yield with 16% ee (Eq. 3). When kinetic resolution of racemic
2-phenylcyclohexanone (6) and bicyclooctanone (8) was ex-
amined, the corresponding lactones (7 and 9) were obtained,
but no asymmetric induction was observed in both the recov-
ered ketones and the produced lactones (Eqs. 4 and 5).
of the Yb atom with both the oxygen atom on the seleninic or
peroxyseleninic acid moiety and the oxygen atom on the silyl
ether moiety might change the structure of a reactive interme-
diate, resulting in an improvement of the enantioselectivity of
3a. Reactions in the presence of diselenide 1b (0.01 molar

Y. Miyake et al.
Bull. Chem. Soc. Jpn., 75, No. 10 (2002) 2235
(2)
(3)
(4)
(5)
Scheme 2. Plausible pathway of asymmetric Baeyer–Villiger
oxidation.
the racemization because of thermodynamical stabilization18
of the peroxyseleninic acid, and so the enantio-enriched γ-lac-
tone is obtained (up to 19% ee). Highly stereoselective forma-
tion of seleninic and peroxyseleninic acids should be essential
for achieving a high asymmetric induction.
Experimental
General Procedures. 1H and 13C-NMR spectra were mea-
sured on JEOL EX-400, JEOL JNM-AL300, and JEOL JNM-
GSX270 spectrometers for solutions in CDCl3 with Me4Si as an
internal standard. GLC analyses were carried out with Shimadzu
GC-14A instrument equipped with a CPB 10-S25-050 (Shimadzu,
fused silica capillary column, 0.33 mm × 25 m, 5.0 mm film
thickness) column using helium as carrier gas. GLC yields were
determined using cyclododecane as an internal standard. HPLC
analyses were carried out on a HITACHI L-7100 with an L-7300
column oven and an L-7400 UV detector using a Daicel Chiralcel
OD column. High-resolution mass spectra (HRMS) were ob-
tained with a JEOL JMS-SX102A spectrometer. Column chro-
matographies were performed with Merck silica gel 60. (4S,5S)-
2-(4-tert-Butyldimethylsiloxymethyl-5-phenyl-2-oxazolinyl)ben-
zene was prepared by the reported method.19
A plausible reaction pathway is shown in Scheme 2. Treat-
ment of (Ar*Se)2 (ꢀ) with H2O2 affords a chiral arylseleninic
acid (ꢁ) which is further oxidized to the corresponding aryl-
peroxyseleninic acid (ꢂ).10d The coordination of the carbonyl
oxygen atom of cyclobutanone and the two oxygen atoms of ꢂ
to the Yb atom (M) generates the intermediate ꢃ. The attack
of the peroxyseleninic acid moiety in ꢃ to the carbonyl carbon
atom gives the intermediate ꢄ followed by the rearrangement
to give the corresponding γ-lactones together with the forma-
tion of ꢁ. Asymmetric induction should occur at the rearrange-
ment step. In our catalytic oxidation system, two diastereoiso-
mers each of seleninic and of peroxyseleninic acid could be
formed because seleninic and peroxyseleninic acids have a tri-
coordinate geometry with central chirality on the selenium at-
om. Not only the chirality on the oxazoline ring but also the
central chirality on the selenium atom may have an effect on
enantioselectivity. Quite recently, Kamigata et al. succeeded
in the optical resolution of racemic seleninic acid and de-
scribed that the racemization of the resolved seleninic acid
proceeded easily in a dilute solution.17 The existence of Se≥N
interaction in the intermediates ꢃ and ꢄ might be expected to
lock the conformation of the intermediates and prevent slightly
Preparation of Bis{2-[(4S,5S)-4-(tert-butyldimethylsiloxy-
methyl)-5-phenyl-2-oxazolinyl]phenyl} Diselenide (1b).
sec-
Butyllithium (23.0 mL of 1.06 M cyclohexane–hexane solution,
24.4 mmol) was added to a stirred solution of (4S,5S)-2-(4-tert-
butyldimethylsiloxymethyl-5-phenyl-2-oxazolinyl)benzene (7.78
g, 21.2 mmol) and N,N,Nꢀ,Nꢀ-tetramethylethylenediamine
(TMEDA) (9.6 mL, 63.6 mmol) in THF (35 mL) at −78 °C. The
resulting red solution was stirred at −78 °C for 15 min, followed
by the addition of selenium powder (1.67 g, 21.2 mmol). The re-
action mixture was allowed to warm to room temperature and
stirred for 4 h under nitrogen. It was then oxidized by stirring un-
der air for 12 h. The resulting brown solution was extracted with
CH2Cl2 (50 mL × 3) and the combined organic phase was dried
over anhydrous MgSO4, filtered and concentrated under reduced
pressure. Purification by recrystallization from methanol afforded
the optically active diselenide 1b (9.80 g, 11.0 mmol, 52% yield):
A yellow solid; mp 83–85 °C; [α]2D5 +40.45 (c 0.50, CHCl3); H
1

2236 Bull. Chem. Soc. Jpn., 75, No. 10 (2002)
Asymmetric Baeyer–Villiger Oxidation
Table 2. Summary of Crystallographic Data of 1c
NMR (400 MHz, CDCl3) δ 0.11 (s, 6H), 0.12 (s, 6H), 0.90 (s,
18H), 3.82–3.87 (m, 2H), 4.07–4.10 (m, 2H), 4.43–4.48 (m, 2H),
5.64 (d, J = 0.49 Hz, 2H), 7.27–7.44 (m, 14H), 7.86–8.00 (m,
4H); 13C NMR (100 MHz, CDCl3) δ −5.11, 18.4, 26.0, 65.1, 83.4,
125.47, 125.52, 125.6, 128.0, 128.6, 129.8, 130.5, 131.5, 133.6,
141.0, 163.4. HRMS m/z found: 893.2194, calcd for C44H57N2O4-
Se2Si2 M+: 893.2199.
Empirical formula
MW
C32H28N2O4Se2
662.50
Crystal syst
Space group
Cryst color
Lattice params
a /Å
monoclinic
P21 (#4)
yellow
Preparation of Bis{2-[(4S,5S)-4-hydroxymethyl-5-phenyl-
oxazolin-2-yl]phenyl} Diselenide (1c). Removal of tert-butyl-
dimethylsilyl protecting group of 1b (1.88 g, 2.10 mmol) was ef-
fected by stirring it with a solution of tetrabutylammonium fluo-
ride (TBAF) (4.4 mL of 1.0 M THF solution, 4.4 mmol) in THF
(20 mL) at room temperature for 8 h. The mixture was poured
into saturated aqueous NH4Cl solution and extracted with CH2Cl2
(15 mL × 3). The organic layer was dried over MgSO4 and con-
centrated under vacuum. The resulting oil was washed with hex-
ane to remove the produced siloxane and the residue was purified
by recrystallization from CH2Cl2/hexane to afford the correspond-
ing diselenide 1c (1.21 g, 1.83 mmol, 87% yield): A pale yellow
solid; mp 99–101 °C; [α]2D5 +6.72 (c 0.52, CHCl3); 1H NMR (400
MHz, CDCl3) δ 3.83 (dd, J = 11.7, 3.9 Hz, 2H), 4.13 (dd, J =
11.7, 3.9 Hz), 4.47–4.51 (m, 2H), 5.57 (d, J = 7.32 Hz, 2H), 7.28–
7.42 (m, 14H), 7.89–7.97 (m, 4H); 13C NMR (100 MHz, CDCl3) δ
64.0, 76.9, 83.0, 125.7, 125.8, 125.9, 128.5, 128.9, 129.9, 130.6,
131.9, 133.7, 140.1, 164.4. HRMS m/z found: 665.0459, calcd for
C32H28N2O4Se2 M+: 665.0465. Found: C, 57.28; H, 4.39; N,
3.73%. Calcd for C32H28N2O4Se2: C, 58.01; H, 4.26; N, 4.23%.
X-ray Structural Analysis of 1c. Single crystals (C32H28N2-
O4Se2) suitable for X-ray analysis were prepared by recrystalliza-
tion from CH2Cl2/hexane. Diffraction data was collected on a
Rigaku RAXIS-RAPID imaging plate area detector with Mo Kα
(λ = 0.71069 Å) radiation and a graphite monochromator at −100
°C. Details of the X-ray diffraction study are summarized in Table
2. For structure analysis and refinement, computations were per-
formed using the CrystalStructure crystallographic software pack-
age.20,21 Neutral atom scattering factors were taken from Ref. 22.
Anomalous dispersion effects were included in Fcalc23; the values
of ∆f ꢀ and ∆f were those of Ref. 24. The structure was solved by
heavy-atom Patterson methods. All non-hydrogen atoms were re-
fined anisotropically. Hydrogen atoms were included, but not re-
fined. The weighting scheme w = 1/σ2(F0) with σ(F0) from
counting statistics gave satisfactory agreement analyses. Crystal-
lographic data have been deposited at the CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK and copies can be obtained on request,
free of charge, by quoting the publication and the deposition num-
bers CCDC-181729. The data are also deposited as Document
No. 75041 at the Office of the Editor of Bull. Chem. Soc. Jpn.
General Procedure for Asymmetric Baeyer–Villiger Oxida-
tion of 3-Phenylcyclobutanone (2a). A mixture of the dise-
lenide 1b (4.5 mg, 0.0050 mmol), Yb(OTf)3 (6.2 mg, 0.010
mmol), pH 7.4 phosphate buffer solution (10 mL), 30% aqueous
H2O2 solution (75 mL) and cyclododecane (as an internal stan-
dard; 50 mg) was stirred for 1 h in THF (0.50 mL) at room tem-
perature under nitrogen. After cooling to 0 °C, a solution of 3-
phenylcyclobutanone 2a (73 mg, 0.50 mmol) in THF (0.50 mL)
was added to the mixture and the resulting mixture was stirred for
24 h. It was then quenched with water (5 mL) and extracted with
diethyl ether. The extract was dried over MgSO4. The amount of
the product 3a25 was determined by GLC analysis. For isolation
of 3a, the solvent was evaporated and the residue was purified by
column chromatography using hexane/ethyl acetate = 5/1 as an
eluent. The ee value of 3a was determined by HPLC analysis with
10.7364(6)
9.1154(4)
b /Å
c /Å
15.5693(8)
104.880(2)
1472.6(1)
β /°
V /Å3
Z
2
Dcalc /g cm−3
µ(Mo Kα) /cm−1
F(000)
1.494
25.50
668.00
Rigaku RAXIS-RAPID
Mo Kα (λ = 0.71069 Å)
graphite monochromated
−100
ω
55.0
3593
2118
Patterson methods
(DIRDIF99 PATTY)
full-matrix least squares
395
5.36
0.037; 0.038
0.10
Diffractometer
Radiation
Temp /°C
Scan type
Max. 2θ (°)
No. of rflns measd
No. of observns (I > 3.00σ(I))
Structure soln
Refinement
No. of variables
Reflection/parameter ratio
Residuals: R ; Rw
Goodness of fit (GOF)
Max shift/error in final cycle
Maximum peak in final
Diff map /e Å−3
0.16
0.55
Maximum peak in final
Diff map /e Å−3
−0.40
a Daicel Chiralcel AD column (eluent: hexane/MeOH = 200/1,
flow rate: 1.0 mL/min, column temperature: 30 °C, retention time:
54.2 min and 60.6 min).
Other lactones (3b,26 3c,27 5,28 7,29 and 930) were obtained from
the corresponding ketones under similar reaction conditions.
This work was supported by a Grant-in-Aid for Scientific
Research (No. 13305062) from the Ministry of Education, Sci-
ence, Sports and Culture.
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