Asymmetric epoxidation of α,β-unsaturated ketones catalyzed by rare-earth metal amides RE[N(SiMe3)2]3with chiral TADDOL ligands

Article abstract of DOI:10.1039/d0nj05228k

The catalytic asymmetric epoxidation of α,β-unsaturated ketones by tert-butylhydroperoxide (TBHP) has been well established using rare-earth metal amides RE[N(SiMe3)2]3 (RE = La(1), Nd(2), Sm(3), Y(4), Yb(5)) with chiral TADDOL ligands. It was found that

Full text of DOI:10.1039/d0nj05228k

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Asymmetric epoxidation of a,b-unsaturated
ketones catalyzed by rare-earth metal amides
RE[N(SiMe3)2]3 with chiral TADDOL ligands†
Cite this: New J. Chem., 2021,
45, 1043
Haiwen Shan, Chengrong Lu,* Bei Zhao * and Yingming Yao
The catalytic asymmetric epoxidation of a,b-unsaturated ketones by tert-butylhydroperoxide (TBHP) has
been well established using rare-earth metal amides RE[N(SiMe3)2]3 (RE = La(1), Nd(2), Sm(3), Y(4), Yb(5))
with chiral TADDOL ligands. It was found that the combination of Yb[N(SiMe3)2]3 and chiral TADDOL ligand
H2L2 ((4S,5S)-2,2-dimethyl-a,a,a0,a0-tetra-3,5-bis(trifluormethylphenyl)-1,3-dioxolane-4,5-dimethanol) in
a
Received 24th October 2020,
Accepted 2nd December 2020
1 : 1 molar ratio was the optimal choice, which provided the desired epoxides in excellent yields (89–99%)
and good to high enantioselectivities (57–94% ee), using DBU as an additive. Various substrates were proved
to have functional group tolerance. In addition, gram-level experiments and derivatization experiments were
also studied.
DOI: 10.1039/d0nj05228k
rsc.li/njc
Introduction
Optically pure compounds have always occupied an important
position in organic synthesis due to their unique drug or
biological activities.1 Direct asymmetric synthesis is the common
and efficient method to achieve optically active compounds.2
Whether the outcomes are good or not mainly depends on the
Fig. 1 Synthesis of TADDOL ligands.
design of the chiral catalysts, namely the core of the asymmetric as 1987, Seebach’s group first reported the synthesis of TAD-
synthesis. TADDOLs are a kind of familiar chiral molecule, DOL ligands; then a series of chiral Ti or Zr complexes with
which are derived from the natural product tartaric acid.3 TADDOLs were successfully developed for asymmetric
They are easily available and tunable from the reaction of chiral catalysis.16 Subsequently, a research boom was set off in chiral
acetals or ketals of tartrate esters with different Grignard TADDOL ligands. In 2001, Shibasaki synthesized a series of
reagents (Fig. 1).4 It is found that TADDOLs themselves serve enantiomerically enriched trans-b-cyanohydrins of cyclohex-
as chiral catalysts in some cases, including aldol reactions,5 enes with the combination of TADDOL and Zr(OiPr)4 in a
Diels–Alder reactions,6 Strecker reactions,7 Wittig reactions,8 one-pot reaction.12b One year later, Renaud explored the
and alkylation reactions.9 However, a relatively large amount of enantioselective Diels–Alder reactions of N-alkoxyacrylates
catalyst (20–30 mol%) and relative long reaction time (48–120 h) and cyclopentadiene in the presence of (iBu)3Al and 1-naphthyl-
are generally required.
TADDOL, and a range of cyclic amide compounds were obtained
To improve the efficiency of asymmetric transformations, with high ee values.13a In 2011, Joshi successfully employed an
the utilization of metal-based catalysts bearing chiral ligands is Mg–TADDOLate catalyst to catalyze the enantioselective addi-
a better strategy.10 It is noticed that the TADDOL molecule tion of RZnX to benzaldehyde.14d So far, the catalytic system Ti–
contains two adjacent diarylhydroxylmethyl groups on a 1,3- TADDOL has been the most studied. In 2001, Charette used
dioxolane ring,11 and that the unique structure is predisposed chiral TADDOL–Ti complexes as catalysts to investigate their
to form chelate complexes via the two hydroxyl groups coordi- application in the asymmetric cyclopropanation of allylic
nated with a central metal (e.g., Zr,12 Al,13 Mg,14 Ti15). As early alcohols. A series of cyclopropylmethanols was synthesized
with good yield (up to 90%) and enantioselectivity (up to
94% ee) under mild conditions.15a In 2012, Matsuyama
employed a Ti–TADDOLate complex as a catalyst to realize
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
People’s Republic of China. E-mail: luchengrong@suda.edu.cn,
the asymmetric Diels–Alder reaction of dihydroquinoline and
zhaobei@suda.edu.cn; Fax: +86-512-65880305; Tel: +86-512-65880305
electrophilic enone to synthesize chiral isoquinoline
derivatives.15g In 2019, Kananovich developed Ti–TADDOLate
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d0nj05228k
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Table 1 Optimization of the model reaction conditionsa
complexes to catalyze asymmetric Kulinkovich cyclopropana-
tion of carboxylic esters with alkenes, which produced the
corresponding cyclopropanols with 84–87% ee.15h Though
metal-based TADDOL complexes have been investigated for
many years, substoichiometric amounts of catalyst are still
indispensable in several examples, and the diversity of metal
species and their reactions need to be further developed.
People generally favor rare-earth metal complexes for their
high reactivities.17 In recent years, our group has focused on
the synthesis of chiral rare-earth metal catalysts and their
applications in asymmetric reactions.18 A series of chiral rare-
earth metal complexes bearing phenoxy-functionalized proli-
nols were synthesized successively, which were proven to be
effective in the asymmetric epoxidation of a,b-unsaturated
ketones,18a,b the Michael addition of malonates to unsaturated
ketones,18c the phospha-Michael reaction of a,b-unsaturated
amide18d and the reduction of ketones.18e The rare-earth metal
complexes combined with chiral salen ligands were found to be
effective in the enantioselective epoxidation of a,b-unsaturated
ketones.18f Very recently, a novel set of rare-earth metal com-
plexes stabilized by Trost ligands were developed, which show
excellent yields and high enantioselectivities in the asymmetric
hydroboration reaction of ketones.18g Encouraged by the above
exhilarating results, novel chiral rare-earth metal catalysts with
TADDOLs were investigated in the asymmetric epoxidation of
a,b-unsaturated ketones, which generates optically pure epox-
ides that are of importance in the synthesis of many natural
products and optically active drugs. Also, further transforma-
tion starting from the optically pure epoxides was tested.
Entry
Cat.
Ligand
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
La-1
La-1
La-1
La-1
La-1
La-1
La-1
La-1
La-1
La-1
La-1
La-1
Nd-2
Sm-3
Y-4
H2L1
H2L2
H2L3
H2L4
H2L5
H2L6
H2L7
H2L8
H2L9
H2L10
H2L11
H2L12
H2L2
H2L2
H2L2
H2L2
99
99
97
99
95
96
89
90
99
99
99
99
99
99
99
97
0
25
20
1
0
11
3
4
9
17
22
21
20
21
14
22
36
10
11
12
13
14
15
16
Yb-5
a
Reactions were performed with chalcone (0.3 mmol) in 2 mL solvent.
b
c
Yields were determined by 1H NMR spectroscopy. Determined by
chiral HPLC analysis.
of other conditions was carried out, including solvent, time,
temperature, additives, the amount of solvent, the amount of
catalyst and the ratio of catalyst to chiral ligand. In general, the
solvent is a significant factor that cannot be ignored when
studying asymmetric catalysis. Commonly used solvents were
Results and discussion
Twelve chiral TADDOL ligands H2Ln were synthesized accord- tested, but no obvious improvement in the enantioselectivity of
ing to the previous work.19 The investigation of lanthanum the reaction was observed in the current system (ESI,† Table S1).
amides La[N(SiMe3)2]3 together with TADDOLs in the epoxida- Acetonitrile was used as the optimal solvent for further screen-
tion of chalcone using tert-butylhydroperoxide (TBHP) as the ing. We tried to shorten or prolong the reaction time, but it had
oxidant was conducted in acetonitrile and the results are listed no significant effect on the ee value of 7a (ESI,† Table S2,
in Table 1. In our preliminary screening of chiral ligands, entries 1–4). It is worth noting that lowering the reaction
chalcones were almost quantitatively converted to the corres- temperature has been confirmed to be effective in several
ponding epoxides 7a, but the enantiomeric excess values of 0– cases.20 To our delight, it works in the current system too.
25% were disappointing (Table 1, entries 1–12). But the use of Although the yield of 7a was sacrificed, the enantioselectivity
TADDOL ligands with electron-withdrawing groups on the was improved to 45% ee when the reaction was conducted at
meta-positions of the phenyl ring had obviously higher enan- ꢀ30 1C (ESI,† Table S2, entries 5–8). Nevertheless, the tempera-
tioselectivities (Table 1, entries 2–5). The modifications on the ture cannot be cooled down further, because the yield of 7a was
ketal moieties, whether acetone, benzophenone or cyclohexa- dramatically decreased, even though the enantioselectivity of
none, do not have a substantial effect on the improvement in the reaction increased slightly at ꢀ40 1C (ESI,† Table S2,
the enantioselectivities of epoxides 7a (Table 1, entries 2, 3, 9, entry 9).
10, 11 and 12). Since the outcome from TADDOL ligand H2L2
The addition of a base in the asymmetric transformation
with 3,5-bistrifluoromethyl groups is relatively better, it is used usually had positive effects on promoting enantioselectivity.21
in the following screening. Different rare-earth metal amides Our previous work also found that the addition of pyridine
were tested and a slight enhancement in ee value for 7a was successfully improved the enantioselectivity of the reduction of
observed when the amide was Yb[N(SiMe3)2]3 (Table 1, entries 2 ketones using ytterbium-based complexes.18e Gratifyingly,
and 13–16).
when a certain amount of pyridine was added to the current
Subsequently, in order to improve the enantioselectivity of system, it gave the desired product 7a in 87% yield with 81% ee
the asymmetric epoxidation of chalcones, the routine screening (Table 2, entry 1). Subsequently, a lot of attempts were made
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N,N,N0,N0-tetramethyl-1,2-ethane-diamine (TMEDA), 1,5,7-triazabicyclo
[4.4.0]dec-5-ene (TBD), and 1,4-diazabicyclo[2.2.2]octane (DABCO)
were ineffective (Table 2, entries 4–7). To our delight, when
the reactions were performed in the presence of 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU), both the yield and ee
value of 7a were significant improved, up to 99% yield and
94% ee (Table 2, entry 8). Finally, the ideal dosage of 30 mol%
DBU was confirmed (Table 2, entries 8–12). Next, routine
screening of the amount of solvent, the amount of catalyst
and the molar ratio of catalyst to ligand was conducted.
Unfortunately, none of these measures worked (ESI,†
Tables S3 and S4). Thus, the optimal reaction conditions in
the asymmetric epoxidation of chalcones with TBHP were
10 mol% of H2L2–Yb[N(SiMe3)2]3 (1 : 1) and 30 mol% DBU in
acetonitrile at ꢀ30 1C for 16 h.
Table
2
The effect of additives on the asymmetric epoxidation of
chalconea
Entry
Additive
y (mol%)
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
Py
30
30
30
30
30
30
30
30
10
20
40
50
87
73
87
90
79
95
54
99
89
99
99
99
81
75
81
12
30
26
23
94
76
78
87
83
4,40-Bipyridine
DMAP
Et3N
TMEDA
TBD
DABCO
DBU
DBU
DBU
9
10
11
12
DBU
DBU
A series of a,b-unsaturated ketones were synthesized and
the substrate scope was studied under the optimal reaction
conditions (Tables 3–5). Most of the a,b-unsaturated ketones
were converted into the corresponding chiral epoxides catalyzed
by a three-component catalyst H2L2–Yb[N(SiMe3)2]3–DBU in high
to excellent yields (89–99%) with good to high enantioselectiv-
ities (57–94% ee). However, alkyl substituted unsaturated
a
Reactions were performed with Yb[N(SiMe3)2]3 (10 mol%), H2L2
(10 mol%), chalcone (0.3 mmol), TBHP (0.36 mmol) in 2 mL CH3CN.
b
c
Yields were determined by 1H NMR spectroscopy. Determined by
chiral HPLC analysis.
with some commonly encountered organic bases. It was found ketones 8p were obtained in excellent yield with poor enantios-
that both 4-(dimethylamino)-pyridine (DMAP) and 4,40- electivity (34% ee). The substituents on the benzene ring at the
bipyridine were also beneficial to the enantioselectivity of the b-position of the unsaturated ketone have no obvious influence
model reaction (Table 2, entries 2 and 3). However, triethylamine, on the yields of the reaction, and the ee values of the products
Table 3 Epoxidation of a,b-unsaturated ketones catalyzed by Yb[N(SiMe3)2]3
Table 4 Epoxidation of a,b-unsaturated ketones catalyzed by Yb[N(SiMe3)2]3
combined with TADDOL ligand H2L2 a
combined with TADDOL ligand H2L2 a
Reactions were performed with Yb[N(SiMe3)2]3 (10 mol%), H2L2
a
a
Reactions were performed with Yb[N(SiMe3)2]3 (10 mol%), H2L2
(10 mol%), DBU (30 mol%), chalcone (0.3 mmol), TBHP (0.36 mmol) (10 mol%), DBU (30 mol%), chalcone (0.3 mmol), TBHP (0.36 mmol)
in 2 mL CH3CN. Yield was determined by 1H NMR spectroscopy. in 2 mL CH3CN. Yield was determined by 1H NMR spectroscopy.
Determined by chiral HPLC analysis.
Determined by chiral HPLC analysis.
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Table 5 Epoxidation of a,b-unsaturated ketones catalyzed by Yb[N(SiMe3)2]3
combined with TADDOL ligand H2L2 a
Scheme 2 The conversion of product 8n to functionalized indan-1-one
derivatives.
Scheme 3 The conversion of product 8n to functionalized 2-
isoxazolidines.
a
Reactions were performed with Yb[N(SiMe3)2]3 (10 mol%), H2L2
(10 mol%), DBU (30 mol%), chalcone (0.3 mmol), TBHP (0.36 mmol)
in 2 mL CH3CN. Yield was determined by 1H NMR spectroscopy.
Determined by chiral HPLC analysis.
vary from 68% to 94%. However, when the para positions of the
b-benzene ring contain a bulky tert-butyl group or strong
electron-withdrawing groups such as nitro or trifluoromethyl,
the ee values decrease (Table 3, 7e, 7i–j). When benzene rings on
the acyl side of the unsaturated ketones have substituents, the
corresponding epoxides are obtained in excellent yields, and the
enantioselectivities are significantly improved, expect for those
ortho-substituted substrates (Table 4, 8h–j). Satisfactorily, the
substrates bearing electron-rich hetero-aromatic rings or
naphthyl groups also transformed to the corresponding epoxides
in excellent yields (89–99%) with high ee values (61–92%)
(Table 4, 8l–o). The substrates modified on both rings were also
investigated in the current system to generate epoxides in
moderate to good stereoselectivities and retaining excellent
yields (Table 5, 9a–h). These results are comparable with our
previous reports on rare-earth metal-catalyzed asymmetric
epoxidation,18a,b,f and are better than those for some other metal
catalysts, including some Ca,22 V,23 Fe,24 Co25 and Zn26-based
catalysts. Moreover, this is the first application of a rare-earth
metal catalyst combined with TADDOL ligands to realize the
asymmetric epoxidation of a,b-unsaturated ketones.
Scheme 4 The conversion of product 8n to a functionalized a-hydroxyl
epoxide.
Crafts alkylation of epoxides, play a central role in the structures
of many natural products, agrochemicals and medicines.27
So the stereoselective synthesis of functionalized 3-phenyl-2-
hydroxyl-1-indanone was tried followed the published
method,28 using epoxide 8n as the starting material. The corres-
ponding products 10 in 99% overall yield, about 80% ee, and
more than 19 : 1 dr value were obtained in just a few minutes
(Scheme 2). Moreover, 2-isoxazolidines 11, which exhibit various
biological activities,29 were obtained via the reaction of epoxide
8n with hydroxylamine hydrochloride in the presence of pyridine
in 98% yield with 80% ee (Scheme 3). Furthermore, a-hydroxyl
epoxide 12, a useful building block in the preparation of
pharmaceutical and natural products,30 is quantitatively
achieved from the reduction of the chiral epoxide 8n with 81%
ee for both diastereomers, and a dr value close to 2 : 1
(Scheme 4). It is meaningful that all the stereochemistries of
the above transformations are maintained.
As shown in Scheme 1, the epoxidation of a,b-unsaturated
ketones on a gram scale proceeded smoothly with a satisfactory
yield and high enantioselectivity with appropriate prolonging
of the reaction time.
On account of the synthetic potential of chiral epoxides,
further transformations were carried out. 3-Aryl-2-hydroxyl-1-
indanones, prepared from a sequential intramolecular Friedel–
Conclusions
In summary, rare-earth metal amides combined with chiral
TADDOL ligands were investigated for the first time in the
asymmetric epoxidation of a,b-unsaturated ketones. After careful
screening, 10 mol% of Yb[N(SiMe3)2]3 together with ligand H2L2
((4S,5S)-2,2-dimethyl-l-a,a,a0,a0-tetra-3,5-bis(trifluormethylphenyl)-
1,3-dioxolane-4,5-dimethanol) in 1:1 molar ratio were proved to
be the optimal catalyst combination with 30 mol% DBU in
acetonitrile at ꢀ30 1C. Many a,b-unsaturated ketones with diverse
substituents were tolerated and the desired epoxides in excellent
yields (89–99%) with good to high enantioselectivities (57–94% ee)
Scheme 1 The amplification reaction of the preparation of compound
8n.
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were obtained. In addition, gram-level experiments and derivati- chromatography with the elution system (ethyl acetate : petroleum
zation experiments were also studied.
ether = 1 : 3).
Experimental procedures for the conversion of product 8n to an
a-hydroxyl epoxide 12
Experimental section
The reaction was performed with epoxide 8n (0.2 mmol, 54.8 mg)
and NaBH4 (0.24 mmol, 7.6 mg) in CH3OH (2.0 mL). The
reaction mixture was stirred at 0 1C for 10 minutes. It was
quenched by adding a saturated solution of NH4Cl, and the
desired product was extracted by ethyl acetate, and purified
using silica gel column chromatography with the elution system
(ethyl acetate: petroleum ether = 1 : 5).
All operations and reactions involving air and water sensitive
components were performed using standard Schlenk technol-
ogy. The substrates, a,b-unsaturated ketones, were synthesized
according to the literature.31 All solvents and liquid compounds
were dried with CaH2 and distilled before use. Flash chromato-
graphy was performed using 200–300 mesh silica gel with a
SepaBean machine instrument. 1H NMR, 19F NMR and 13C
NMR spectra were recorded in CDCl3 on a Bruker AV-400
apparatus. ESI-HRMS spectra were obtained on a Bruker ESI-
TOF (with methanol as solvent). Enantiomeric excesses were
determined by chiral HPLC analysis on a SHIMADZU LC-20AD
instrument equipped with a quaternary pump, employing a
Daicel Chiralcel column at 35 1C. Optical rotations were
measured in acetone or chloroform using an SGW-2 Polari-
meter at 20 1C. The absolute configurations of the epoxides
were determined by comparing the specific rotation with the
literature data as cited. Melting points were recorded on an
Electrothermal Engineering Limited 8100.
Spectroscopic data for asymmetric epoxidation products
((2R,3S)-3-Phenyloxiran-2-yl)-phenylmethanone (7a)32d
.
A
white powder, 66.6 mg, yield 99%; [a]2D0 = ꢀ1071 (c 0.25, in
acetone); 1H NMR (400 MHz, CDCl3) d 8.04–7.96 (m, 2H, Ar-H),
7.61 (dd, J = 11.7 Hz, J = 4.3 Hz, 1H, Ar-H), 7.48 (t, J = 7.9 Hz, 2H,
Ar-H), 7.43–7.33 (m, 5H, Ar-H), 4.31 (d, J = 1.9 Hz, 1H, CH), 4.07
(d, J = 1.8 Hz, 1H, CH); 13C NMR (101 MHz, CDCl3) d 193.1,
135.5, 135.4, 134.0, 129.1, 128.9, 128.8, 128.3, 125.8, 61.0, 59.4;
i
94% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH,
1.0 mL minꢀ1, 14.0 min (major), 20.1 min (minor); HRMS (ESI-
MS) m/z [M + Na]+ calcd for C15H12O2Na: 247.0735, found:
247.0733. Mp: 74–76 1C.
General procedure for the epoxidation reactions
((2R,3S)-3-(4-Methphenyl)oxiran-2-yl)-phenylmethanone
(7b)32d. A white powder, 68.6 mg, yield 96%, [a]2D0 = ꢀ1041
Under an argon atmosphere, ytterbium amide Yb[N(SiMe3)2]3
(0.03 mmol, 19.60 mg) and DBU (0.09 mmol, 13.5 mL) were
added to a solution of H2L2 (0.03 mmol, 30.30 mg) in CH3CN
(1 mL). After stirring for 30 min at room temperature, oxidant
TBHP (0.36 mmol) was added and the mixture was cooled to
ꢀ30 1C to be stirred for a further 30 min. Afterwards, unsatu-
rated ketone (0.3 mmol) in CH3CN (1 mL) was added to the
mixture and the reaction maintained for 16 h at ꢀ30 1C. Then
the reaction was quenched by adding a saturated solution of
Na2SO3. The desired product was extracted by ethyl acetate,
and purified with silica gel column chromatography with the
elution system (ethyl acetate : petroleum ether = 1 : 10).
1
(c 0.21, in acetone); H NMR (400 MHz, CDCl3) d 8.01 (dd, J =
8.4 Hz, J = 1.2 Hz, 2H, Ar-H), 7.65–7.59 (m, 1H, Ar-H), 7.49 (t, J =
7.7 Hz, 2H, Ar-H), 7.24 (q, J = 8.0 Hz, 4H, Ar-H), 4.29 (d, J =
1.9 Hz, 1H, CH), 4.04 (d, J = 1.8 Hz, 1H, CH), 2.38 (s, 3H, CH3);
13C NMR (101 MHz, CDCl3) d 193.2, 139.0, 135.5, 134.0, 132.4,
129.5, 128.9, 128.3, 125.8, 61.0, 59.5, 21.3; 90% ee, HPLC Daicel
i
IE column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1, 15.3 min
(major), 7.3 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd
for C16H14O2Na: 261.0891, found: 261.0889. Mp: 76-77 1C.
((2R,3S)-3-(4-Methoxyphenyl)oxiran-2-yl)-phenylmethanone
(7c)32d. A white powder, 73.2 mg, yield 96%; [a]2D0 = ꢀ1471
(c 0.19, in acetone); 1H NMR (400 MHz, CDCl3) d 8.04–7.97
(m, 2H, Ar-H), 7.61 (d, J = 7.4 Hz, 1H, Ar-H), 7.48 (t, J = 7.7 Hz,
2H, Ar-H), 7.32–7.27 (m, 2H, Ar-H), 6.96–6.90 (m, 2H, Ar-H),
4.29 (d, J = 1.9 Hz, 1H, CH), 4.02 (d, J = 1.8 Hz, 1H, CH), 3.83
(s, 3H, OCH3); 13C NMR (101 MHz, CDCl3) d 193.2, 160.3, 135.5, 133.9,
Experimental procedures for the conversion of product 8n to
indan-1-one derivatives 10
In a dry tube, TiCl4 (0.02 mmol, 3.8 mg) was added to a solution
of epoxide 8n (0.2 mmol, 54.8 mg) in CH2Cl2 (2 mL) at 0 1C.
After TLC monitoring, the reaction was quenched by adding a
saturated solution of Na2CO3. The desired product was
extracted by CH2Cl2, and purified from silica gel column
chromatography with the elution system (ethyl acetate : petro-
leum ether = 1 : 10).
128.8, 128.3, 127.3, 127.2, 114.2, 61.0, 59.4, 55.4; 85% ee, HPLC
i
Daicel OD-H column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1
,
9.7 min (minor), 10.7 min (major); HRMS (ESI-MS) m/z
[M + Na]+ calcd for C16H14O3Na: 277.0841, found: 277.0840.
Mp: 81–82 1C.
((2R,3S)-3-(4-Isopropylphenyl)oxiran-2-yl)-phenylmethanone
(7d)32b. A colorless oil, 75.9 mg, yield 95%; [a]2D0 = ꢀ1351 (c 0.19,
in acetone); 1H NMR (400 MHz, CDCl3) d 8.03–7.98 (m, 2H),
Experimental procedures for the conversion of product 8n to
2-isoxazolidines 11
The reaction was performed with epoxide 8n (0.2 mmol, 54.8 mg), 7.61 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.7 Hz, 2H), 7.28 (q, J = 8.5 Hz,
pyridine (1.8 mmol, 146 mL) and NH2OHꢁHCl (0.3 mmol, 20.8 mg) 4H), 4.31 (d, J = 1.9 Hz, 1H), 4.05 (d, J = 1.8 Hz, 1H), 1.26 (d, J =
in EtOH (2.0 mL). After refluxing for 2 h, the reaction was 6.9 Hz, 6H); 13C NMR (101 MHz, CDCl3) d 193.2, 150.0, 135.5,
quenched by adding a solution of 1 M HCl. The desired product 133.9, 132.8, 128.8, 128.3, 126.9, 125.9, 61.0, 59.5, 33.9, 23.9;
i
was extracted by ethyl acetate, and purified using silica gel column 85% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH,
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12.2 min (major), 12.7 min (minor); HRMS (ESI-MS) m/z 9.6 min (major), 10.3 min (minor); HRMS (ESI-MS) m/z
[M + Na]+ calcd for C18H18O2Na: 289.1204, found: 289.1201. [M + Na]+ calcd for C16H11F3O2Na: 315.0609, found: 315.0610.
((2R,3S)-3-(4-Tertiarybutylphenyl)oxiran-2-yl)-phenylmethanone Mp: 108–109 1C.
(7e)32d. A colorless oil, 79.9 mg, yield 95%; [a]2D0 = ꢀ1081 (c 0.16,
((2R,3S)-3-(4-Nitrophenyl)oxiran-2-yl)-phenylmethanone
1
in acetone); H NMR (400 MHz, CDCl3) d 8.02 (dd, J = 8.4, J = (7j)22. A pale yellow powder, 74.3 mg, yield 92%; [a]D20 = ꢀ931
1
1.2 Hz, 2H, Ar-H), 7.61 (d, J = 7.4 Hz, 1H, Ar-H), 7.51–7.40 (c 0.16, in acetone); H NMR (400 MHz, CDCl3) d 8.26 (d, J =
(m, 4H, Ar-H), 7.32 (d, J = 8.3 Hz, 2H, Ar-H), 4.32 (d, J = 1.9 Hz, 8.8 Hz, 2H, Ar-H), 8.04–7.96 (m, 2H, Ar-H), 7.65 (t, J = 7.4 Hz,
1H, CH), 4.06 (d, J = 1.8 Hz, 1H, CH), 1.34 (s, 9H, C(CH3)3); 1H, Ar-H), 7.58–7.48 (m, 4H, Ar-H), 4.28 (d, J = 1.8 Hz, 1H, CH),
13C NMR (101 MHz, CDCl3) d 193.2, 152.3, 135.5, 133.9, 132.4, 4.21 (d, J = 1.6 Hz, 1H, CH); 13C NMR (101 MHz, CDCl3) d 192.0,
128.8, 128.3, 125.7, 125.6, 60.9, 59.4, 34.7, 31.3; 70% ee, HPLC 148.3, 142.7, 135.2, 134.3, 129.0, 128.4, 126.6, 124.0, 60.8, 58.0;
Daicel OD-H column, 90% hexanes, 10% iPrOH, 1.0 mL minꢀ1
,
75% ee, HPLC Daicel OD-H column, 90% hexanes, 10% iPrOH,
5.5 min (minor), 6.3 min (major); HRMS (ESI-MS) m/z [M + H]+ 1.0 mL minꢀ1, 23.0 min (minor), 26.8 min (major); HRMS (ESI-
calcd for C19H21O2: 281.1542, found: 281.1544.
MS) m/z [M + Na]+ calcd for C15H11NO4Na: 292.0586, found:
((2R,3S)-3-(4-Fluorophenyl)oxiran-2-yl)-phenylmethanone 292.0583. Mp: 140–141 1C.
(7f)32d. A white powder, 66.8 mg, yield 92%; [a]2D0 = ꢀ1201
((2R,3S)-3-(2-Methphenyl)oxiran-2-yl)-phenylmethanone
1
(c 0.26, in acetone); H NMR (400 MHz, CDCl3) d 8.01 (dd, J = (7k)26. A white powder, 63.6 mg, yield 89%; [a]D20 = ꢀ781 (c 0.19,
8.3, 1.2 Hz, 2H), 7.67–7.59 (m, 1H), 7.49 (dd, J = 10.7, 4.8 Hz, in acetone); 1H NMR (400 MHz, CDCl3) d 8.05 (dd, J = 8.3,
2H), 7.38–7.31 (m, 2H), 7.10 (t, J = 8.6 Hz, 2H), 4.26 (d, J = 1.2 Hz, 2H, Ar-H), 7.63 (d, J = 7.4 Hz, 1H, Ar-H), 7.52 (dd, J =
1.9 Hz, 1H), 4.07 (d, J = 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) 10.9 Hz, J = 4.5 Hz, 2H, Ar-H), 7.37–7.32 (m, 1H, Ar-H), 7.27 (dt,
d 192.9, 164.4, 161.9, 135.4, 134.1, 131.2, 131.2, 128.9, 128.3, J = 6.0 Hz, J = 2.9 Hz, 2H, Ar-H), 7.22–7.17 (m, 1H, Ar-H), 4.22
127.6, 127.5, 116.0, 115.7, 60.9, 58.8; 19F NMR (377 MHz, CDCl3) (dd, J = 5.4 Hz, J = 1.9 Hz, 2H, CH), 2.37 (s, 3H, CH3); 13C NMR
d ꢀ112.2; 79% ee, HPLC Daicel IC column, 90% hexanes, 10% (101 MHz, CDCl3) d 193.3, 136.3, 135.4, 134.0, 133.9, 130.1,
iPrOH, 1.0 mL minꢀ1, 13.8 min (major), 14.4 min (minor); 128.9, 128.5, 128.3, 126.4, 124.2, 60.1, 57.7, 18.8; 90% ee, HPLC
HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H11FO2Na: 265.0641, Daicel IE column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1
,
i
found: 265.0639. Mp: 91–94 1C.
11.2 min (major), 20.9 min (minor); HRMS (ESI-MS) m/z
((2R,3S)-3-(4-Chlorophenyl)oxiran-2-yl)-phenylmethanone [M + Na]+ calcd for C16H14O2Na: 261.0891, found: 261.0892.
(7g)32c. A white powder, 73.7 mg, yield 95%, [a]2D0 = ꢀ1341 Mp: 70–72 1C.
1
(c 0.25, in acetone); H NMR (400 MHz, CDCl3) d 8.02 (d, J =
((2R,3S)-3-(2-Methoxyphenyl)oxiran-2-yl)-phenylmethanone
8.0 Hz, 2H, Ar-H), 7.65 (t, J = 7.4 Hz, 1H, Ar-H), 7.59–7.47 (7l)26. A white powder, 73.2 mg, yield 96%; [a]D20 = ꢀ1261 (c 0.21,
(m, 4H, Ar-H), 7.27 (d, J = 8.4 Hz, 2H, Ar-H), 4.27 (d, J = 1.7 Hz, in acetone); 1H NMR (400 MHz, CDCl3) d 8.12–8.00 (m, 2H, Ar-
1H, CH), 4.07 (s, 1H, CH); 13C NMR (101 MHz, CDCl3) d 192.9, H), 7.61 (s, 1H, Ar-H), 7.48 (t, J = 7.7 Hz, 2H, Ar-H), 7.37–7.28
164.4, 161.9, 135.4, 134.1, 131.3, 131.2, 128.9, 128.3, 127.6, (m, 2H, Ar-H), 6.99 (s, 1H, Ar-H), 6.91 (d, J = 8.2 Hz, 1H, Ar-H),
127.5, 115.9, 115.7, 60.9, 58.8; 86% ee, HPLC Daicel OD-H 4.39 (d, J = 1.8 Hz, 1H, CH), 4.19 (d, J = 2.0 Hz, 1H, CH), 3.82
i
column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1, 8.2 min (s, 3H, OCH3); 13C NMR (101 MHz, CDCl3) d 193.6, 158.2, 135.6,
(minor), 9.0 min (major); HRMS (ESI-MS) m/z [M + Na]+ calcd 133.8, 129.7, 128.8, 128.4, 125.5, 124.1, 120.8, 110.3, 60.4, 55.8,
for C15H11ClO2Na: 281.0345, found: 281.0346. Mp: 114–115 1C. 55.3; 92% ee, HPLC Daicel OD-H column, 90% hexanes, 10%
((2R,3S)-3-(4-Bromophenyl)oxiran-2-yl)-phenylmethanone iPrOH, 1.0 mL minꢀ1, 8.1 min (minor), 9.7 min (major); HRMS
(7h)22. A white powder, 89.0 mg, yield 98%, [a]2D0 = ꢀ1251 (c 0.19, (ESI-MS) m/z [M + Na]+ calcd for C16H14O3Na: 277.0841, found:
in acetone); 1H NMR (400 MHz, CDCl3) d 8.05–7.95 (m, 2H, 277.0841. Mp: 89–90 1C.
Ar-H), 7.62 (d, J = 7.4 Hz, 1H, Ar-H), 7.49 (t, J = 7.7 Hz, 2H, Ar-H),
((2R,3S)-3-(2-Fluorophenyl)oxiran-2-yl)-phenylmethanone
7.38–7.31 (m, 2H, Ar-H), 7.13–7.04 (m, 2H, Ar-H), 4.26 (d, J = (7m)25. A colorless oil, 69.1 mg, yield 95%; [a]D20 = ꢀ1761 (c 0.27,
1.8 Hz, 1H, CH), 4.07 (d, J = 1.7 Hz, 1H, CH); 13C NMR in acetone); 1H NMR (400 MHz, CDCl3) d 8.07–7.98 (m, 2H),
(101 MHz, CDCl3) d 192.8, 164.4, 161.9, 135.4, 134.0, 131.3, 7.66–7.58 (m, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.40–7.29 (m, 2H),
131.2, 128.9, 128.3, 127.6, 127.5, 115.9, 115.7, 60.9, 58.8; 7.19 (t, J = 7.3 Hz, 1H), 7.09 (dd, J = 10.3, 8.6 Hz, 1H), 4.34 (d, J =
i
79% ee, HPLC Daicel IC column, 90% hexanes, 10% PrOH, 1.5 Hz, 1H), 4.30 (d, J = 1.9 Hz, 1H); 13C NMR (101 MHz, CDCl3)
1.0 mL minꢀ1, 13.8 min (major), 14.4 min (minor); HRMS d 192.8, 162.8, 160.3, 135.3, 134.1, 130.4, 130.3, 128.9, 128.3,
(ESI-MS) m/z [M + Na]+ calcd for C15H11BrO2Na: 324.9840, 126.4, 126.4, 124.6, 124.5, 122.9, 115.6, 115.4, 59.9, 54.2, 54.1;
found: 324.9841. Mp: 89–90 1C.
19F NMR (377 MHz, CDCl3) d ꢀ120.0; 90% ee, HPLC Daicel IE
i
((2R,3S)-3-(4-Trifluorophenyl)oxiran-2-yl)-phenylmethanone
column, 90% hexanes, 10% PrOH, 13.4 min (major), 16.3 min
(7i)22. A white powder, 84.1 mg, yield 96%; [a]2D0 = ꢀ1531 (c 0.21, (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H11FO2Na:
in acetone); 1H NMR (400 MHz, CDCl3) d 8.03–7.98 (m, 2H), 265.0641, found: 265.0644.
7.65 (dd, J = 16.3, 7.8 Hz, 3H), 7.55–7.48 (m, 4H), 4.27 (d, J =
((2R,3S)-3-(2-Chlorophenyl)oxiran-2-yl)-phenylmethanone
1.7 Hz, 1H), 4.15 (d, J = 1.1 Hz, 1H); 13C NMR (101 MHz, CDCl3) (7n)25. A colorless oil, 73.7 mg, yield 95%; [a]2D0 = ꢀ1091 (c 0.32,
d 192.4, 139.6, 135.3, 134.2, 129.0, 128.4, 126.1, 125.8, 125.8, in acetone); 1H NMR (400 MHz, CDCl3) d 8.05 (d, J = 8.5 Hz, 2H),
60.9, 58.4; 19F NMR (377 MHz, CDCl3) d ꢀ62.7; 68% ee, HPLC 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 7.43–7.37 (m, 2H),
i
Daicel IC column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1
,
7.32 (dd, J = 8.1, 1.2 Hz, 2H), 4.40 (d, J = 1.8 Hz, 1H), 4.17
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Paper
(d, J = 1.9 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 192.8, 135.3, 135.6, 133.0, 129.5, 129.0, 128.7, 128.5, 125.8, 60.9, 59.3, 21.8;
i
134.0, 133.7, 133.3, 129.7, 129.3, 128.9, 128.4, 127.3, 126.1, 60.0, 90% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH,
57.1; 84% ee, HPLC Daicel IC column, 90% hexanes, 10% iPrOH, 17.4 min (major), 25.7 min (minor); HRMS (ESI-MS) m/z
11.7 min (major), 12.1 min (minor); HRMS (ESI-MS) m/z [M + Na]+ [M + Na]+ calcd for C16H14O3Na: 277.0841, found: 277.0843.
calcd for C15H11ClO2Na: 281.0345, found: 281.0345.
Mp: 77–78 1C.
((2R,3S)-3-(3-Methoxyphenyl)oxiran-2-yl)-phenylmethanone
((2R,3S)-4-Fluorophenyl-3-phenyloxiran-2-yl)-methanone
(7o)26. A colorless oil, 73.2 mg, yield 96%; [a]2D0 = ꢀ1231 (c 0.23, (8c)32d. A white powder, 66.8 mg, yield 92%; [a]D20 = ꢀ1151
in acetone); 1H NMR (400 MHz, CDCl3) d 8.04–7.95 (m, 2H, (c 0.27, in acetone). 1H NMR (400 MHz, CDCl3) d 8.09–8.00
Ar-H), 7.61 (t, J = 7.4 Hz, 1H, Ar-H), 7.48 (t, J = 7.7 Hz, 2H, Ar-H), (m, 2H, Ar-H), 7.38 (ddd, J = 7.8 Hz, J = 6.2 Hz, J = 2.3 Hz, 5H,
7.31 (t, J = 7.8 Hz, 1H, Ar-H), 6.97 (d, J = 7.6 Hz, 1H, Ar-H), 6.93– Ar-H), 7.16 (t, J = 8.6 Hz, 2H, Ar-H), 4.24 (d, J = 1.8 Hz, 1H, CH),
6.87 (m, 2H, Ar-H), 4.28 (d, J = 1.9 Hz, 1H, CH), 4.05 (d, J = 4.07 (d, J = 1.7 Hz, 1H, CH), 13C NMR (101 MHz, CDCl3) d 191.6,
1.8 Hz, 1H, CH), 3.82 (s, 3H, OCH3); 13C NMR (101 MHz, CDCl3) 167.5, 135.3, 131.9, 131.8, 131.2, 131.1, 129.1, 128.8, 125.8,
d 193.0, 160.0, 137.1, 135.4, 134.0, 129.9, 128.9, 128.3, 118.2, 116.2, 116.0, 61.0, 59.3; 19F NMR (377 MHz, CDCl3) d ꢀ103.0;
i
114.7, 110.9, 60.9, 59.3, 55.3; 89% ee, HPLC Daicel OD-H 94% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH,
i
column, 90% hexanes, 10% PrOH, 1.0 mL minꢀ1, 8.9 min 11.2 min (major), 16.4 min (minor); HRMS (ESI-MS) m/z
(minor), 9.9 min (major); HRMS (ESI-MS) m/z [M + Na]+ calcd [M + Na]+ calcd for C15H11FO2Na: 265.0641, found: 265.0639.
for C16H14O3Na: 277.0841, found: 277.0841.
Mp: 83–84 1C.
((2R,3S)-3-(3-Chlorophenyl)oxiran-2-yl)-phenylmethanone
((2R,3S)-4-Chlorophenyl-3-phenyloxiran-2-yl)-methanone
(7p)26. A white powder, 76.8 mg, yield 99%; [a]2D0 = ꢀ1291 (c 0.28, (8d)32d. A white powder, 75.3 mg, yield 97%; [a]D20 = ꢀ1141
in acetone); 1H NMR (400 MHz, CDCl3) d 8.05 (dd, J = 8.4, (c 0.41, in acetone); 1H NMR (400 MHz, CDCl3) d 8.00–7.94
1.2 Hz, 2H, Ar-H), 7.63 (t, J = 7.4 Hz, 1H, Ar-H), 7.50 (t, J = 7.7 Hz, (m, 2H, Ar-H), 7.49–7.44 (m, 2H, Ar-H), 7.38 (ddd, J = 8.7 Hz, J =
2H, Ar-H), 7.44–7.37 (m, 2H, Ar-H), 7.33 (dt, J = 5.2 Hz, J = 7.1 Hz, J = 4.6 Hz, 5H, Ar-H), 4.23 (d, J = 1.9 Hz, 1H, CH), 4.07
3.7 Hz, 2H, Ar-H), 4.41 (d, J = 1.9 Hz, 1H, CH), 4.17 (d, J = 1.9 Hz, (d, J = 1.8 Hz, 1H, CH); 13C NMR (101 MHz, CDCl3) d 192.0,
1H, CH); 13C NMR (101 MHz, CDCl3) d 192.6, 137.6, 135.3, 140.6, 135.2, 133.7, 129.8, 129.2, 129.1, 128.8, 125.8, 61.0, 59.4;
i
134.9, 134.1, 130.1, 129.2, 128.9, 128.3, 125.7, 124.1, 60.7, 58.55; 94% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH,
i
81% ee, HPLC Daicel IC column, 90% hexanes, 10% PrOH, 11.6 min (major), 18.0 min (minor); HRMS (ESI-MS) m/z
13.5 min (major), 14.5 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H11ClO2Na: 281.0345, found: 281.0346.
[M + Na]+ calcd for C15H11ClO2Na: 281.0345, found: 281.0346. Mp: 116 1C.
Mp: 74–75 1C.
((2R,3S)-4-Bromophenyl-3-phenyloxiran-2-yl)-methanone
((2R,3S)-3-(3-Bromophenyl)oxiran-2-yl)-phenylmethanone (8e)32d. A white powder, 89.1 mg, yield 98%; [a]D20 = ꢀ1201
(7q)32c. A colorless oil, 87.3 mg, yield 96%; [a]D20 = ꢀ1741 (c 0.34, (c 0.27, in acetone); 1H NMR (400 MHz, CDCl3) d 7.92–7.85
in acetone); 1H NMR (400 MHz, CDCl3) d 8.00 (dd, J = 5.2, (m, 2H, Ar-H), 7.66–7.59 (m, 2H, Ar-H), 7.37 (m, J = 8.0, 7.0,
3.3 Hz, 2H), 7.68–7.60 (m, 1H), 7.54–7.47 (m, 4H), 7.33–7.25 4.6 Hz, 5H, Ar-H), 4.23 (d, J = 1.9 Hz, 1H, CH), 4.07 (d, J = 1.8 Hz,
(m, 2H), 4.26 (d, J = 1.8 Hz, 1H), 4.05 (d, J = 1.8 Hz, 1H); 1H, CH); 13C NMR (101 MHz, CDCl3) d 192.2, 135.2, 134.1,
13C NMR (101 MHz, CDCl3) d 192.6, 137.9, 135.3, 134.1, 132.1, 132.2, 129.8, 129.4, 129.1, 128.8, 125.8, 61.0, 59.4; 88% ee,
i
130.3, 128.9, 128.6, 128.4, 124.6, 123.0, 60.8, 58.4; 71% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH, 12.4 min
i
HPLC Daicel IC column, 90% hexanes, 10% PrOH, 12.7 min (major), 19.8 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd
(major), 14.1 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H11BrO2Na: 324.9840, found: 324.9842. Mp: 126–127 1C.
for C15H11BrO2Na: 324.9840, found: 324.9834.
((2R,3S)-4-Nitrophenyl-3-phenyloxiran-2-yl)-methanone (8f)22.
((2R,3S)-4-Methphenyl-3-phenyloxiran-2-yl)-methanone (8a)32d
.
A pale yellow powder, 79.1 mg, yield 98%; [a]2D0 = ꢀ941 (c 0.19, in
A white powder, 70.8 mg, yield 99%; [a]2D0 = ꢀ1041 (c 0.28, in acetone); H NMR (400 MHz, CDCl3) d 8.32 (d, J = 8.8 Hz, 2H),
1
1
acetone); H NMR (400 MHz, CDCl3) d 7.92 (d, J = 8.2 Hz, 2H, 8.18 (d, J = 8.8 Hz, 2H), 7.44–7.34 (m, 5H), 4.27 (d, J = 1.7 Hz,
Ar-H), 7.38 (d, J = 4.4 Hz, 5H, Ar-H), 7.31–7.27 (m, 2H, Ar-H), 1H), 4.10 (d, J = 1.5 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 192.2,
4.28 (d, J = 1.9 Hz, 1H, CH), 4.07 (d, J = 1.8 Hz, 1H, CH), 2.42 150.7, 139.6, 134.7, 129.5, 129.4, 128.9, 125.8, 124.0, 61.4, 59.6;
(s, 3H, CH3); 13C NMR (101 MHz, CDCl3) d 192.6, 145.1, 135.6, 82% ee, HPLC Daicel IC column, 90% hexanes, 10% iPrOH, 1.0
133.0, 129.6, 129.0, 128.7, 128.5, 125.8, 60.9, 59.3, 21.8; mL minꢀ1, 28.3 min (minor), 30.2 min (major); HRMS (ESI-MS)
85% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH, m/z [M + Na]+ calcd for C15H11NO4Na: 292.0586, found:
i
17.4 min (major), 25.5 min (minor); HRMS (ESI-MS) m/z 292.0582. Mp: 118–120 1C.
[M + Na]+ calcd for C16H14O2Na: 261.0891, found: 261.0894.
Mp: 87–88 1C.
((2R,3S)-4-Cyanophenyl-3-phenyloxiran-2-yl)-methanone (8g)32b
.
A white powder, 72.5 mg, yield 97%; [a]2D0 = ꢀ1311 (c 0.23, in
1
((2R,3S)-4-Methoxyphenyl-3-phenyloxiran-2-yl)-methanone acetone); H NMR (400 MHz, CDCl3) d 8.11 (d, J = 8.6 Hz, 2H),
(8b)32d. A white powder, 75.5 mg, yield 99%; [a]2D0 = ꢀ971 (c 0.12, 7.79 (d, J = 8.6 Hz, 2H), 7.41 (dd, J = 5.2, 2.0 Hz, 3H), 7.35 (dd, J =
in acetone); 1H NMR (400 MHz, CDCl3) d 7.92 (d, J = 8.2 Hz, 2H, 7.2, 2.6 Hz, 2H), 4.24 (d, J = 1.8 Hz, 1H), 4.08 (d, J = 1.8 Hz, 1H);
Ar-H), 7.39 (d, J = 4.6 Hz, 5H, Ar-H), 7.28 (d, J = 8.0 Hz, 2H, 13C NMR (101 MHz, CDCl3) d 192.3, 138.2, 134.8, 132.7, 129.3,
Ar-H), 4.28 (d, J = 1.9 Hz, 1H, CH), 4.07 (d, J = 1.8 Hz, 1H, CH), 128.9, 128.8, 125.7, 117.6, 117.2, 61.3, 59.6; 91% ee, HPLC Daicel
2.43 (s, 3H, OCH3); 13C NMR (101 MHz, CDCl3) d 192.6, 145.1, IE column, 80% hexanes, 20% PrOH, 16.5 min (major), 37.5 min
i
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(minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for C16H11NO2Na:
272.0687, found: 272.0681. Mp: 115–116 1C.
[(2R,3S)-3-Phenyloxiran-2-yl](furan-2-yl)-methanone (8m)25
.
A pale yellow powder, 61.7 mg, yield 96%; [a]2D0 = ꢀ1321
1
((2R,3S)-2-Methphenyl-3-phenyloxiran-2-yl)-methanone (8h)26. (c 0.10, in acetone); H NMR (400 MHz, CDCl3) d 7.67 (d, J =
A colorless oil, 70.7 mg, yield 99%; [a]2D0 = ꢀ761 (c 0.17, in 1.0 Hz, 1H, CH), 7.45 (d, J = 3.6 Hz, 1H, CH), 7.41–7.31 (m, 5H,
1
acetone); H NMR (400 MHz, CDCl3) d 7.70 (d, J = 7.8 Hz, 1H), Ar-H), 6.59 (d, J = 3.6 Hz, 1H, CH), 4.14 (s, 2H, CH); 13C NMR
7.40 (d, J = 4.6 Hz, 6H), 7.33–7.26 (m, 2H), 4.13 (d, J = 1.8 Hz, (101 MHz, CDCl3) d 182.0, 151.2, 147.6, 135.3, 129.0, 128.7,
1H), 4.06 (d, J = 1.8 Hz, 1H), 2.57 (s, 3H); 13C NMR (101 MHz, 125.8, 119.5, 112.7, 60.6, 59.6; 92% ee, HPLC Daicel IE column,
i
CDCl3) d 196.5, 138.9, 135.4, 135.3, 132.3, 132.0, 129.1, 129.0, 90% hexanes, 10% PrOH, 20.1 min (major), 25.5 min (minor);
128.8, 125.8, 125.8, 62.4, 59.5, 21.0; 57% ee, HPLC Daicel IE HRMS (ESI-MS) m/z [M + Na]+ calcd for C13H10O3Na: 237.0528,
i
column, 90% hexanes, 10% PrOH, 12.3 min (major), 20.7 min found: 237.0532. Mp: 44–47 1C.
(minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for C16H14O2Na:
((2R,3S)-Naphthyl-2-yl-3-phenyloxiran-2-yl)-methanone (8n)25.
261.0891, found: 261.0893.
A white powder, 73.2 mg, yield 89%; [a]2D0 = ꢀ681 (c 0.18, in
((2R,3S)-2-Fluorophenyl-3-phenyloxiran-2-yl)-methanone (8i)25. acetone); H NMR (400 MHz, CDCl3) d 8.56 (s, 1H, Ar-H), 8.06
1
A colorless oil, 71.9 mg, yield 99%; [a]2D0 = ꢀ1761 (c 0.27, in (d, J = 1.7 Hz, 1H, Ar-H), 7.97–7.86 (m, 3H, Ar-H), 7.67–7.53
1
acetone); H NMR (400 MHz, CDCl3) d 7.91 (t, J = 7.5 Hz, 1H), (m, 2H, Ar-H), 7.43 (s, 5H, Ar-H), 4.44 (d, J = 1.9 Hz, 1H, CH),
7.57 (dd, J = 13.2, 7.7 Hz, 1H), 7.38 (s, 5H), 7.28 (t, J = 7.6 Hz, 4.17 (d, J = 1.8 Hz, 1H, CH); 13C NMR (101 MHz, CDCl3) d 192.9,
1H), 7.13 (dd, J = 10.5, 8.1 Hz, 1H), 4.31 (dd, J = 4.3, 1.8 Hz, 1H), 135.9, 135.6, 132.8, 132.4, 130.4, 129.7, 129.1, 129.0, 128.9,
4.07 (d, J = 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 192.1, 128.8, 127.9, 127.1, 125.9, 123.6, 61.0, 59.5; 86% ee, HPLC
i
163.5, 161.0, 135.8, 135.4, 130.6, 129.0, 128.6, 125.9, 124.8, Daicel IE column, 90% hexanes, 10% PrOH, 20.0 min (major),
116.8, 63.0, 59.9; 19F NMR (377 MHz, CDCl3) d ꢀ109.3; 83% 27.6 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for
ee, HPLC Daicel IE column, 90% hexanes, 10% iPrOH, 14.5 min
(major), 17.6 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd
for C15H11FO2Na: 265.0641, found: 265.0639.
C
19H14O2Na: 297.0891, found: 297.0889. Mp: 110–113 1C.
((2R,3S)-Naphthyl-1-yl-3-phenyloxiran-2-yl)-methanone (8o)25.
A colorless oil, 75.7 mg, yield 92%; [a]2D0 = ꢀ1091 (c 0.27, in
((2R,3S)-2-Chlorophenyl-3-phenyloxiran-2-yl)-methanone (8j)26. acetone); H NMR (400 MHz, CDCl3) d 8.70 (d, J = 8.7 Hz, 1H),
A colorless oil, 76.8 mg, yield 99%; [a]2D0 = ꢀ1421 (c 0.24, in 8.04 (d, J = 8.2 Hz, 1H), 7.97 (dd, J = 7.2, 1.1 Hz, 1H), 7.93–7.87
acetone); 1H NMR (400 MHz, CDCl3) d 7.64–7.60 (m, 1H), 7.49– (m, 1H), 7.64 (ddd, J = 8.5, 6.9, 1.5 Hz, 1H), 7.60–7.54 (m, 1H),
7.41 (m, 2H), 7.39–7.33 (m, 6H), 4.16 (d, J = 1.8 Hz, 1H), 4.10 7.49 (dd, J = 8.1, 7.3 Hz, 1H), 7.41 (s, 5H), 4.27 (d, J = 1.8 Hz, 1H),
(d, J = 1.7 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 196.3, 136.5, 4.16 (d, J = 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 196.2,
135.2, 133.0, 132.2, 130.4, 130.1, 129.0, 128.7, 127.2, 125.8, 135.4, 133.9, 133.8, 132.9, 130.3, 129.1, 129.0, 128.8, 128.6,
62.9, 60.5; 77% ee, HPLC Daicel IE column, 90% hexanes, 10% 128.5, 126.8, 125.9, 125.5, 124.4, 62.6, 59.7; 61% ee, HPLC
1
iPrOH, 13.2 min (major), 18.7 min (minor); HRMS (ESI-MS) Daicel IE column, 90% hexanes, 10% PrOH, 17.9 min (major),
i
m/z [M + Na]+ calcd for C15H11ClO2Na: 281.0345, found: 21.3 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for
281.0348.
C
19H14O2Na: 297.0891, found: 297.0889.
((2R,3S)-3-Methoxyphenyl-3-phenyloxiran-2-yl)-methanone
((2R,3S)-2,2-Dimethyl-1-yl-3-phenyloxiran-2-yl)-propan-1-one
(8k)32e. A white powder, 74.0 mg, yield 97%; [a]2D0 = ꢀ1281 (8p)32a. A colorless oil, 75.7 mg, yield 99%; [a]D20 = ꢀ511 (c 0.38,
1
(c 0.33, in acetone); H NMR (400 MHz, CDCl3) d 8.00 (dd, J = in acetone); 1H NMR (400 MHz, CDCl3) d 7.99 (dd, J = 8.3,
8.4 Hz, J = 1.2 Hz, 2H, Ar-H), 7.60 (d, J = 7.4 Hz, 1H, Ar-H), 1.2 Hz, 2H), 7.59 (d, J = 7.4 Hz, 1H), 7.48 (t, J = 7.7 Hz, 2H), 4.11
7.48 (t, J = 7.7 Hz, 2H, Ar-H), 7.30 (dd, J = 11.8 Hz, J = 4.0 Hz, 1H, (d, J = 2.2 Hz, 1H), 2.94 (d, J = 2.2 Hz, 1H), 1.02 (s, 9H); 13C NMR
Ar-H), 7.01–6.94 (m, 1H, Ar-H), 6.93–6.88 (m, 2H, Ar-H), (101 MHz, CDCl3) d 195.0, 135.5, 133.8, 128.8, 128.1, 67.6, 54.8,
4.28 (d, J = 1.9 Hz, 1H, CH), 4.05 (d, J = 1.8 Hz, 1H, CH), 3.82 31.3, 25.7; 34% ee, HPLC Daicel IC column, 90% hexanes, 10%
(s, 3H, OCH3); 13C NMR (101 MHz, CDCl3) d 193.0, 160.0, 137.1, iPrOH, 9.8 min (major), 10.5 min (minor); HRMS (ESI-MS) m/z
135.4, 134.0, 129.9, 128.9, 128.3, 118.2, 114.7, 110.9, 60.9, 59.3, [M + Na]+ calcd for C13H16O2Na: 227.1048, found: 227.1051.
55.3; 89% ee, HPLC Daicel OD-H column, 90% hexanes, 10%
(2R,3S)-4-Methylphenyl-3-(4-methylphenyl)-2-oxiran-methanone
iPrOH, 8.9 min (minor), 9.9 min (major); HRMS (ESI-MS) m/z (9a)18a. A white powder, 71.9 mg, yield 95%; [a]D20 = ꢀ1251
[M + Na]+ calcd for C16H14O3Na: 277.0841, found: 277.0843. (c 0.23, in acetone); H NMR (400 MHz, CDCl3) d 7.92 (d, J =
1
Mp: 74–76 1C.
8.2 Hz, 2H, Ar-H), 7.32–7.24 (m, 4H, Ar-H), 7.22 (d, J = 8.1 Hz,
[(2R,3S)-3-Phenyloxiran-2-yl](thien-2-yl)-methanone (8l)25. A 2H, Ar-H), 4.28 (d, J = 1.9 Hz, 1H, CH), 4.04 (d, J = 1.8 Hz,
pale yellow powder, 68.4 mg, yield 99%; [a]2D0 = ꢀ1241 (c 0.13, in 1H, CH), 2.43 (s, 3H, CH3), 2.39 (s, 3H, CH3); 13C NMR
1
acetone); H NMR (400 MHz, CDCl3) d 7.99 (d, J = 3.8 Hz, 1H, (101 MHz, CDCl3) d 192.7, 145.0, 139.0, 133.0, 132.6, 129.5,
CH), 7.73 (d, J = 4.9 Hz, 1H, CH), 7.41–7.32 (m, 5H, Ar-H), 7.21– 129.4, 128.4, 125.8, 60.9, 59.4, 21.8, 21.2; 73% ee, HPLC Daicel
7.14 (m, 1H, CH), 4.16 (d, J = 1.5 Hz, 1H, CH), 4.08 (d, J = 1.6 Hz, IE column, 90% hexanes, 10% iPrOH, 18.5 min (major),
1H, CH); 13C NMR (101 MHz, CDCl3) d 186.4, 140.9, 135.2, 21.5 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for
133.6, 129.1, 128.7, 128.5, 125.8, 61.9, 59.4; 86% ee, HPLC
C
17H16O2Na: 275.1048, found: 275.1048. Mp: 101–103 1C.
(2R,3S)-4-Methylphenyl-3-(4-tert-butylphenyl)-2-oxiran-metha-
i
Daicel IE column, 90% hexanes, 10% PrOH, 14.8 min (major),
24.1 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd for none (9b)18a. A colorless oil, 81.8 mg, yield 93%; [a]D20 = ꢀ1341
C
13H10O2SNa: 253.0299, found: 253.0301. Mp: 54–56 1C.
(c 0.25, in acetone); 1H NMR (400 MHz, CDCl3) d 7.98 (d, J = 8.2 Hz,
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2H, Ar-H), 7.49 (d, J = 8.4 Hz, 2H, Ar-H), 7.35 (d, J = 8.2 Hz, 4H, 133.5, 132.0, 129.8, 129.3, 127.4, 123.2, 60.9, 58.7; 78% ee,
i
Ar-H), 4.36 (d, J = 1.9 Hz, 1H, CH), 4.11 (d, J = 1.8 Hz, 1H, CH), HPLC Daicel IE column, 90% hexanes, 10% PrOH, 14.8 min
2.48 (s, 3H, CH3), 1.40 (s, 9H, C(CH3)3); 13C NMR (101 MHz, (major), 27.5 min (minor); HRMS (ESI-MS) m/z [M + Na]+ calcd
CDCl3) d 192.7, 152.2, 145.0, 133.1, 132.6, 129.5, 128.5, 125.7, for C15H10BrClO2Na: 358.9450, found: 358.9452. Mp: 128–
125.6, 60.8, 59.3, 34.7, 31.3, 21.8; 81% ee, HPLC Daicel OD-H 130 1C.
i
column, 90% hexanes, 10% PrOH, 5.2 min (minor), 5.8 min
(2R,3S)-4-Chlorophenyl-3-(3-bromophenyl)-2-oxiran-methanone
(major); HRMS (ESI-MS) m/z [M + H]+ calcd for C20H23O2: (9h)32c. A colorless oil, 97.2 mg, yield 96%; [a]D20 = ꢀ1391 (c 0.46,
295.1698, found: 295.1698.
in acetone); 1H NMR (400 MHz, CDCl3) d 7.96 (d, J = 8.6 Hz, 2H),
(2R,3S)-4-Methoxyphenyl-3-(4-methylphenyl)-2-oxiran-methanone 7.49 (dd, J = 14.2, 8.8 Hz, 4H), 7.32–7.25 (m, 2H), 4.19 (d, J =
(9c)32c. A white powder, 76.5 mg, yield 95%; [a]2D0 = ꢀ1291 1.8 Hz, 1H), 4.05 (d, J = 1.8 Hz, 1H); 13C NMR (101 MHz, CDCl3)
1
(c 0.22, in acetone); H NMR (400 MHz, CDCl3) d 7.83 (d, J = d 191.6, 140.8, 137.6, 133.5, 132.2, 130.4, 129.8, 129.3, 128.6,
8.9 Hz, 2H), 7.06 (d, J = 13.4 Hz, 4H), 6.78 (d, J = 8.9 Hz, 2H), 124.5, 123.0, 60.8, 58.4; 90% ee, HPLC Daicel IE column, 90%
4.08 (d, J = 1.9 Hz, 1H), 3.86 (d, J = 1.8 Hz, 1H), 3.70 (s, 3H), 2.21 hexanes, 10% iPrOH, 11.0 min (major), 28.6 min (minor);
(s, 3H); 13C NMR (101 MHz, CDCl3) d 191.5, 164.2, 138.9, 132.6, HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H10BrClO2Na:
130.7, 129.4, 128.6, 125.8, 114.1, 60.9, 59.2, 55.5, 21.2; 79% ee, 358.9450, found: 358.9451.
i
HPLC Daicel IE column, 90% hexanes, 10% PrOH, 32.5 min
(2R,3S)-2-Hydroxy-3-phenyl-2,3-dihydro-1H-cyclopenta[b]
(major), 36.8 min (minor); HRMS (ESI-MS) m/z [M + H]+ calcd naphthalen-1-one (10)28b. A white powder, 54.3 mg, yield 99%;
for C17H17O3: 269.1178, found: 269.1176. Mp: 87–89 1C.
[a]2D0 = ꢀ191 (c 0.54, in CHCl3); 1H NMR (400 MHz, CDCl3) d 8.47
(2R,3S)-4-Methoxyphenyl-3-(2-methylphenyl)-2-oxiran-methanone (s, 1H), 8.00 (t, J = 3.1 Hz, 2H), 7.97–7.93 (m, 1H), 7.69 (dd, J =
(9d)18a. A colorless oil, 76.5 mg, yield 95%; [a]2D0 = ꢀ961 (c 0.25, 8.1, 1.3 Hz, 1H), 7.66–7.58 (m, 3H), 7.40 (ddd, J = 15.4, 7.8,
in acetone); 1H NMR (400 MHz, CDCl3) d 7.99–7.86 (m, 2H), 6.3 Hz, 3H), 5.59 (dd, J = 7.4, 2.3 Hz, 1H), 5.37 (d, J = 2.3 Hz, 1H),
7.21 (dd, J = 6.7, 2.3 Hz, 1H), 7.17–7.09 (m, 2H), 7.09–7.04 4.27 (d, J = 7.4 Hz, 1H); 13C NMR (101 MHz, CDCl3) d 197.7,
(m, 1H), 6.90–6.79 (m, 2H), 4.08 (d, J = 1.8 Hz, 1H), 4.04 (d, J = 138.2, 136.0, 132.4, 130.9, 130.6, 129.7, 129.3, 128.9, 128.7,
2.0 Hz, 1H), 3.76 (s, 3H), 2.23 (s, 3H); 13C NMR (101 MHz, 128.0, 127.4, 123.9, 76.2, 64.1; 419 : 1 dr determined by HPLC
i
CDCl3) d 191.6, 164.3, 136.3, 134.1, 130.7, 130.1, 128.5, 128.4, Daicel IE column, 90% hexanes, 10% PrOH, minor product:
126.3, 124.2, 114.1, 59.9, 57.5, 55.6, 18.8; 78% ee, HPLC Daicel 80% ee, 12.5 min (minor), 13.8 min (major), major product:
IE column, 90% hexanes, 10% iPrOH, 13.9 min (minor), 81% ee, 15.2 min (minor), 18.3 min (major); HRMS (ESI-MS)
25.5 min (major); HRMS (ESI-MS) m/z [M + H]+ calcd for m/z [M + Na]+ calcd for C19H14O2Na: 297.0891, found: 297.0895.
C
17H17O3 : 269.1178, found: 269.1174.
Mp: 114–116 1C.
(2R,3S)-4-Methoxyphenyl-3-(4-chlorophenyl)-2-oxiran-methanone
(4S,5R)-3-(Naphthalen-2-yl)-5-phenyl-4,5-dihydroisoxazol-
(9e)32c. A white powder, 82.3 mg, yield 95%; [a]2D0 = ꢀ1561 4-ol (11)29b. A white powder, 56.7 mg, yield 98%; [a]D20 = ꢀ341
1
1
(c 0.17, in acetone); H NMR (400 MHz, CDCl3) d 7.96 (d, J = (c 0.13, in CHCl3); H NMR (400 MHz, DMSO) d 8.31 (s, 1H),
8.6 Hz, 2H), 7.46 (d, J = 8.6 Hz, 2H), 7.28 (d, J = 8.7 Hz, 2H), 6.93 7.98 (s, 2H), 7.95 (dd, J = 4.8, 2.8 Hz, 2H), 7.60–7.53 (m, 2H),
(d, J = 8.7 Hz, 2H), 4.23 (d, J = 1.7 Hz, 1H), 4.02 (d, J = 1.5 Hz, 7.44–7.30 (m, 5H), 6.65 (d, J = 7.1 Hz, 1H), 5.54 (d, J = 6.7 Hz,
1H), 3.83 (s, 3H); 13C NMR (101 MHz, CDCl3) d 192.2, 160.4, 1H), 5.51 (d, J = 3.4 Hz, 1H); 13C NMR (101 MHz, DMSO) d 158.2,
140.5, 133.7, 129.8, 129.2, 127.2, 127.1, 114.2, 61.1, 59.4, 55.4; 139.2, 133.9, 133.1, 129.2, 129.1, 128.6, 128.2, 127.8, 127.3,
i
84% ee, HPLC Daicel IE column, 90% hexanes, 10% PrOH, 126.2, 124.3, 90.1, 83.6; 80% ee, HPLC Daicel IC column, 90%
18.9 min (major), 28.0 min (minor); HRMS (ESI-MS) m/z hexanes, 10% iPrOH, 11.5 min (minor), 15.1 min (major);
[M + Na]+ calcd for C16H12ClO3Na: 311.0451, found: 311.0457. HRMS (ESI-MS) m/z [M + Na]+ calcd for C15H10BrClO2Na:
Mp: 97–98 1C.
312.1000, found: 312.1006. Mp: 204–206 1C.
(2R,3S)-4-Methoxyphenyl-3-(3-chlorophenyl)-2-oxiran-methanone
(S)-Naphthalen-2-yl-((2R,3S)-3-phenyloxiran-2-yl)methanol
(9f)32c. A colorless oil, 80.6 mg, yield 93%; [a]2D0 = ꢀ1451 (c 0.20, (12)30b. A white powder, 54.7 mg, yield 99%; [a]D20 = ꢀ101 (c 0.14,
in acetone); 1H NMR (400 MHz, CDCl3) d 7.91 (d, J = 9.0 Hz, 2H), in CHCl3); 1H NMR (400 MHz, CDCl3) d 7.90–7.79 (m, 4H), 7.53
7.27–7.20 (m, 3H), 7.17 (s, 1H), 6.86 (d, J = 9.0 Hz, 2H), 4.12 (dd, J = 8.5, 1.6 Hz, 1H), 7.50–7.42 (m, 2H), 7.36–7.17 (m, 5H),
(d, J = 1.9 Hz, 1H), 3.95 (d, J = 1.8 Hz, 1H), 3.78 (s, 3H); 13C NMR 5.13 (d, J = 2.7 Hz, 0.75H), 4.86 (s, 0.25H), 4.16 (d, J = 2.1 Hz,
(101 MHz, CDCl3) d 190.8, 164.3, 137.9, 134.9, 130.8, 130.0, 0.75H), 4.04 (d, J = 2.1 Hz, 0.25H), 3.38–3.36 (m, 0.25H), 3.36–
129.1, 128.4, 125.7, 124.1, 114.1, 60.6, 58.3, 55.6; 86% ee, HPLC 3.33 (m, 0.75H), 2.81 (d, J = 5.1 Hz, 0.25H), 2.70 (s, 0.75H); 13C
i
Daicel IE column, 90% hexanes, 10% PrOH, 14.8 min (major), NMR (101 MHz, CDCl3) d 137.6, 136.7, 136.5, 136.3, 133.4,
27.5 min (minor); HRMS (ESI-MS) m/z [M + H]+ calcd for 133.3, 133.2, 128.8, 128.7, 128.6, 128.5, 128.4, 128.3, 128.2,
C
16H13ClO3: 311.0451, found: 311.0457.
128.1, 128.0, 127.8, 126.4, 126.3, 126.2, 126.1, 125.8, 125.7,
(2R,3S)-4-Chlorophenyl-3-(4-bromophenyl)-2-oxiran-methanone 125.3, 124.2, 124.1, 73.5, 71.4, 65.7, 65.0, 56.9, 55.2; 2.1 : 1 dr
(9g)18a. A white powder, 100.3 mg, yield 99%; [a]2D0 = ꢀ1491 determined by HPLC Daicel IA column, 80% hexanes, 20%
1
(c 0.42, in acetone); H NMR (400 MHz, CDCl3) d 7.95 (d, J = iPrOH, major product: 81% ee, 8.1 min (minor), 9.1 min
8.7 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.7 Hz, 2H), 7.23 (major), minor product: 81% ee, 9.7 min (minor), 10.1 min
(d, J = 8.4 Hz, 2H), 4.18 (d, J = 1.8 Hz, 1H), 4.04 (d, J = 1.7 Hz, (major); HRMS (ESI-MS) m/z [M + Na]+ calcd for C19H16O2Na:
1H); 13C NMR (101 MHz, CDCl3) d 191.7, 140.7, 134.3, 299.1048, found: 299.1043. Mp: 132–134 1C.
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13 (a) O. Corminboeuf and P. Renaud, Org. Lett., 2002, 4,
1735–1738; (b) M. G. Vinogradov, L. S. Gorshkova,
G. V. Chel’tsova, V. A. Pavlov, I. V. Razmanov, V. A.
Ferapontov, O. R. Malyshev and G. L. HeiseRuss, Russ.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
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J. Neudorfl and B. Goldfuss, J. Organomet. Chem., 2008,
693, 2139–2146; (d) T. Zhang, Y. X. Luan, S. J. Zheng,
Q. Peng and M. C. Ye, Angew. Chem., Int. Ed., 2020, 59,
7439–7443.
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Grant No. 21572151), the
project of scientific and technologic infrastructure of Suzhou
(SZS201708), and Priority Academic Program Development of
Jiangsu Higher Education Institutions.
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