Sulfur-mediated allylic C-H arylation, epoxidation, and aziridination

Article abstract of DOI:10.1021/acs.joc.9b01438

Transition-metal-free, sulfur-mediated allylic C-H arylation, epoxidation, and aziridination were realized through one-pot procedures. The reaction design involved initial addition between olefins and triflic anhydride activated sulfoxides, followed by subsequent reactions of the allylic sulfur ylides generated under basic conditions with arylboronic acids, aldehydes, or aldimines, to give allylic arylation, epoxidation, or aziridination products, respectively.

Full text of DOI:10.1021/acs.joc.9b01438

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Featured Article
Sulfur Mediated Allylic C-H Arylation, Epoxidation and Aziridination
Hang Luo, Gang Hu, and Pingfan Li
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01438 • Publication Date (Web): 09 Jul 2019
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Sulfur-Mediated Allylic C-H Arylation, Epoxidation and Aziridination
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Hang Luo,† Gang Hu,†,‡ and Pingfan Li*,†
†State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing
University of Chemical Technology, Beijing 100029, China
‡Department of Chemistry, Baotou Teacher’s College, Baotou 014030, China
Supporting Information Placeholder
ABSTRACT: Transition-metal-free, sulfur mediated allylic C-H arylation, epoxidation and aziridination were realized through one-
pot procedures. The reaction design involved initial addition between olefins and triflic anhydride activated sulfoxides, followed by
subsequent reactions of the allylic sulfur ylides generated under basic conditions with arylboronic acids, aldehydes, or aldimines, to
give allylic arylation, epoxidation or aziridination products, respectively.
INTRODUCTION
The C–C bond formation at allylic positions has been an
attractive research topic for decades.1 Apart from Alder ene
type reactions, the most influential method for allylic
functionalization is arguably the Tsuji-Trost type allylation.
While palladium-catalyzed allylic substitutions enabled the
synthesis of a broad range of molecules,2 seminal studies on
palladium-catalyzed allylic C-H alkylation provided new
opportunity for converting C-H bond directly to C-C bond at
allylic positions.3 In addition, oxidative cross-dehydrogenative
coupling reaction was another alternative for allylic C-H
functionalization.4 However, reports on allylic C-H arylation
reactions were still rare in the literature, while most metal-
catalyzed coupling of allyl electrophiles with aryl-partners
required functionalized olefins.5 Nakamura and co-workers
realized iron-catalyzed allylic arylation of simple olefins with
aryl-Grignard reagents.6 MacMillan and Cuthbertson
accomplished the direct arylation of allylic C-H bond by using
cyanoarenes as coupling partner via dual photoredox and
Scheme 1. Sulfur mediated allylic C-H arylation,
organocatalysis.7 Rueping's group reported direct allylic
epoxidation, and aziridination reactions
arylation of olefins with aryl- and vinylbromides by the
combined use of nickel and visible light catalysis.8 Recently,
Glorius and co-workers explored rhodium catalyzed allyl-aryl
since the pioneering work by Johnson, Corey and Chaykovsky
Sulfur ylides have been widely used for synthetic chemistry
in the 1960s.11a-d Conventionally, there are two main methods
for generating sulfur ylides: deprotonation of sulfonium salts,
which are usually prepared through sulfide substitution of alkyl
halides; or alternatively, reaction between sulfides and metal
carbenoids, which could be generated from metal-catalyzed
coupling of arylboron reagents or heteroarenes with
unfunctionalized olefins.9 Herein, we report a transition-metal-
free, sulfur mediated route for converting allylic C-H bond to
C-C bond via the allylic sulfur ylide intermediates, which
provides the arylation, epoxidation and aziridination products
in one-pot fashion (Scheme 1).10
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decomposition of diazo compounds. Certain other strategies for
RESULT AND DISCUSSION
the synthesis of sulfur ylides have also been explored.11e-
hAllylic and benzylic sulfur ylides, classified as semi-stabilized
ylides, generally exhibited good reactivity in epoxidation or
aziridination reactions with carbonyl or imine type
compounds.12 Asymmetric reaction of chiral sulfur ylides are
also well-established.11a,11b,13 On the other hand, sulfur ylides
could also react with organoboron reagents through 1,2-
metalate shift of the corresponding ate complex.14 In 2018,
Huang and co-workers further achieved sulfide catalyzed cross-
coupling between benzyl halides and arylboronic acids.15a
Wang’s group also reported a non-transition-metal catalyzed
coupling between benzyl halides and arylboronic acids via
Friedel-Crafts-type reaction pathway.15b
We initially optimized the conditions for allylic C-H
arylation of α-methylstyrene (1a) (Table 1). The formation of
allylic sulfonium salt through electrophilic addition between α-
methylstyrene (1a) and triflic anhydride activated sulfoxides (2)
took place in step 1. After that, boronic acid 3a and base were
added to complete the transformation in step 2. It was found that
inorganic base worked better than strong organic base (i.e. DBU,
entry 1) for this transformation, affording desired product 4aa
(entries 2-4) at room temperature. Instead of dichloromethane
(DCM), toluene or dichloroethane (DCE) could also be used as
solvent for this reaction, and thus allowing increased reaction
temperature for step 2 (entries 5-7, 12). Although higher
temperature exhibited the potential of promoting yields, it also
facilitated other competitive side reactions. In order to avoid the
major side product, which was formed through [3,3]-
sigmatropic rearrangement of allylic sulfonium intermediates
and then rearomatization (Table 2C),16f,16i we tried using
different sulfoxides bearing either electron-donating or
electron-withdrawing groups at the phenyl rings’ para-position
(entries 8-11). Gratifyingly, it was found that bis(4-
chlorophenyl) sulfoxide (2c) could adequately suppress such
unintended rearrangement. When reaction concentration was
lowered to 0.2 M, such optimal condition achieved 92% yield
of arylation product 4aa (entry 13).
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Based on many precedents for the reactions with alkenes and
alkynes involving activated sulfoxides,16,17 we hypothesize that
allylic sulfur ylides could be directly generated from simple
olefins, through electrophilic addition of activated sulfoxides
with olefins, followed by subsequent deprotonation, which
could then react with arylboronic acids via 1,2-metalate shift
and hydrolysis, or with aldehydes/aldimines via Corey-
Chaykovsky reaction, to give the desired allylic functionalized
products (Scheme 1).
Table 1. Optimization of reaction conditions
We then explored the substrate scope of different arylboronic
acids (Table 2A) under the optimized conditions. This arylation
protocol worked nicely for electron-rich arylboronic acids, e.g.
para-alkyloxy substrates gave the corresponding products 4aa-
4ae in 82% to 92% yields, while less electron-rich arylboronic
acids gave products 4af, 4ag, and 4ai with lower yields. For
electron-rich heterocyclic boronic acids, furan-3-boronic acid
only gave desired product 4ah in 35% yield. Halogen
substituted products 4al and 4am were obtained in 56% and 62%
yields, respectively. However, arylboronic acids with strong
electron-withdrawing groups gave no desired product (see
supporting information for details). Protodeboronation of those
boronic acids was predominant under our current reaction
conditions. Presumably, 1,2-migration of the aryl group on
boron-ate complex (see our proposed reaction mechanism in
Scheme 1) would be less favored for electron-deficient aryl
groups. Next, we evaluated a variety of substituted α-
methylstyrenes, and the desired products 4ba-4ha were isolated
in 42% to 86% yields (Table 2B). In addition, isoprene (1k) and
cyclohexene (1n) could also afford the coupling products 4ka
and 4na in 37% and 31% yields, respectively. For alkenes 1l
and 1m with exocyclic methylene groups, it was found that
entry sulfoxide
base
Solvent T (oC) yielda (%)
1b
DBU
DCM
rt
0
2a
2b
3b
4b
K2HPO4ꞏ2H2O
Cs2CO3
DCM
DCM
rt
rt
18
21
<5
36
42
48
77
62
88
<5
64
92
80
2a
2a
KOH
DCM
rt
2a
5
6
LiOHꞏ2H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
K3PO4ꞏ3H2O
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
DCE
rt
2a
2a
2a
2b
2b
2c
2d
2c
2c
2c
rt
7
110
110
150
110
110
80
8
9c
bis(4-methoxylphenyl)
sulfoxide
(2b)
favored
this
transformation, since its electron-rich aryl group on the sulfur
atom probably enhanced the stability of corresponding
sulfonium intermediate. Furthermore, tri-substituted alkenes
failed to give the desired products (see supporting information
for details), presumably, the corresponding allylic sulfur ylides
formed from tri-substituted olefins were steric hindered to
participate in these reactions.
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12d
13e
14f
Toluene
Toluene
110
110
Reaction conditions: a solution of 1a (0.4 mmol) and sulfoxide (2)
in 1 mL of solvent was treated Tf2O (0.48 mmol) at 0 ºC, added
base (1 mmol) and 4-methoxylphenyl boronic acid (1 mmol), and
warmed up, stirred for overnight. aIsolated yield after column
chromatography. bInstead of adding Tf2O at 0 ºC, step 1 was
conducted at - 78 ºC. cMicrowave heating in a sealed tube. dInstead
of adding Tf2O at 0 ºC, step 1 was conducted at - 43 ºC. eUsing 2
mL solvent (0.2 M in 1a). fReaction conducted on 1 mmol scale.
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Table 2. Allylic C-H arylationa
Table 3. Allylic C-H epoxidationa and aziridinationb
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aIsolated yields. bDCE was used instead of toluene as solvent, heated at 80
oC. cUsed sulfoxide 2b instead of 2c.
Reaction conditions:
a solution of alkenes 1 (0.4 mmol) and
For the allylic C-H epoxidation or aziridination reactions,
another set of reaction condition was optimized, and DBU was
found to be most suitable base for generating sulfur ylides in
situ to participate in the Corey-Chaykovsky type reactions (see
supporting information for details). The substrate scope and
side reactions are shown in Table 3. Electron-deficient aromatic
aldehydes afforded the major trans-epoxides 6ab-6ag in
moderate yields with 3:1-4:1 dr (Table 3A). Meta-methoxy
substituted aromatic aldehyde only gave 31% yield of trans-6ai.
When trying some electron-rich aromatic aldehydes, the
corresponding allylic epoxide products were prone to
decompose under acidic condition. Meanwhile, a variety of
electron-rich and electron-deficient α-methylstyrenes 1a-1j
were also tolerated, affording the major trans-epoxides
products in 24% to 65% yields with moderate dr (Table 3B). In
addition, Isoprene (1k) afforded major trans-6kg in 46% with
excellent dr. The use of alkenes 1l and 1m with exocyclic
methylene group afforded trans- 6lg and trans-6mg in lower
yields with poor dr. We tried to enhance the diastereoselectivity
by using different sulfoxides, but achieved no significant
improvement (see supporting information for details). Similarly,
diphenylsulfoxide (2a) in 2 mL of CH2Cl2 was treated Tf2O (0.48 mmol) at
- 78 °C, added DBU (0.96 mmol) and aldehydes (5) or N-tosyl aldimines
(6) (0.6 mmol), warmed up slowly to rt, stirred overnight. The dr (trans :
cis) was determined by crude 1H NMR analysis. Isolated yields of trans-
a
b
isomers. MeCN was used as solvent instead of CH2Cl2, and the reaction
temperature was initially -43 °C, isolated yields for the mixture of two
diastereomers were given.
N-tosyl aldimines provided allylic aziridination products 8aa-
8aj in moderate yields and dr (Table 3C). In those cases, ring
expansion rearrangement of allylic aziridine products toward
dihydropyrroles partly contributed to the diminished yields
(Table 3D).18
In conclusion, we have developed a novel sulfur mediated
allylic C-H functionalization strategy to access arylation,
epoxidation or aziridination products without the involvement
of transition metal or photoredox catalysts, which complements
our previous reports on sulfur mediated allylic/propargylic C-H
alkylation reactions.17a,17c The use of readily available reagents
under robust reaction condition is an attractive feature of this
chemistry involving triflic anhydride activated sulfoxides.
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combined organic phases were dried with Na2SO4 and
concentrated under reduced pressure to give the crude products
for further purification.
EXPERIMENTAL SECTION
General Information. All reactions were carried out in oven-
dried glassware under a nitrogen atmosphere employing
standard techniques unless otherwise noted. Dichloromethane
was refluxed over CaH2, and freshly distilled prior to use. Flash
column chromatography was performed using silica gel
(normal phase, 200-300 mesh). Petroleum ether used for
column chromatography were 60-90 oC fraction, and the
removal of residue solvent was accomplished under rotovap
with repeated azeotrope with chloroform, and then evaporation
under vacuum (< 1 mmHg pressure). Reactions were monitored
by thin-layer chromatography on silica gel 60-F254 coated 0.2
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Methoxy-4-(2-phenylallyl)benzene (4aa): yellow oil (92%, 82
mg), Rf = 0.43 (petroleum ether/dichloromethane = 3:1), was
synthesized according to General Procedure A. 1 mmol scale
reaction for compound 4aa was similarly conducted using 118
mg (1 mmol) α-methylstyrene (1a) to yield 179 mg product 4aa
(80% yield); 1H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.2 Hz,
2H), 7.31 – 7.19 (m, 3H), 7.13 (d, J = 8.5 Hz, 2H), 6.80 (d, J =
8.6 Hz, 2H), 5.46 (s, 1H), 5.00 (s, 1H), 3.77 (m, 5H); 13C{1H}
NMR (100 MHz, CDCl3) δ 158.3, 147.7, 141.3, 131.9, 130.2,
128.6, 127.8, 126.5, 114.6, 114.1, 55.6, 41.1;IR (KBr) ν (cm-1)
2931, 1611, 1511, 1246, 1177, 1036, 899, 818, 780, 702;
HRMS (ESI) calcd for C16H17O+[M+H]+ m/z 225.1274, found
225.1281.
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1
mm plates. The plates were visualized under UV light. H and
13C NMR spectra were recorded on a 400 MHz spectrometer,
usually in CDCl3 with TMS as an internal standard, and the
chemical shifts (δ) were reported in parts per million (ppm). The
IR spectra (KBr pellets, v [cm−1]) were taken on a FTIR
spectrometer. HRMS measurements were carried out on a TOF
mass spectrometer. Substituted alkenes 1b,19 1c, 19 1d, 19 1e, 19
1f, 19 1g,20 1h,19 1i,21 1j,19 1l,17a 1m,17a and sulfoxide substrates
2b,22 2d,22 N-tosylaldimines substrates 7a,23 7b,24 7c,24 7d,25
7e,24 7f,24 7g,23 7h,24 7i24 were known compounds, and prepared
according to published procedures.
1-Ethoxy-4-(2-phenylallyl)benzene (4ab): yellow oil (87%,
83 mg), Rf = 0.43 (petroleum ether/dichloromethane = 3:1), was
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synthesized according to General Procedure A; H NMR (400
MHz, CDCl3) δ 7.42 (d, J = 7.4 Hz, 2H), 7.30 – 7.18 (m, 3H),
7.11 (d, J = 8.4 Hz, 2H), 6.79 (d, J = 8.4 Hz, 2H), 5.45 (s, 1H),
4.99 (s, 1H), 3.97 (q, J = 7.0 Hz, 2H), 3.76 (s, 2H), 1.37 (t, J =
7.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 157.7, 147.7,
141.3, 131.7, 130.2, 128.6, 127.7, 126.5, 114.7, 114.6, 63.7,
41.1, 15.2; IR (KBr) ν (cm-1) 3031, 2979, 2906, 1611, 1582,
1477, 922, 899, 780, 740; HRMS (ESI) calcd for C17H19O+
[M+H]+ m/z 239.1430, found 239.1430.
Preparation of N-tosylaldimine 7j: To the solution of the 4-
(methylthio)benzaldehyde (5 mmol, 1 equiv) in PhMe (30 mL)
was added TsNH2 (5 mmol, 1 equiv) and BF3ꞏEt2O (0.06 ml,
0.5 mmol, 0.1 equiv). The mixture was refluxed using a Dean-
Stark apparatus for 20 hours in an oil bath. After the reaction
was complete as monitored by TLC, the solution was cooled to
room temperature, concentrated under reduced pressure, and
recrystallized from EtOAc/Hexanes to give 0.61 g (40% yield)
7j as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.95 (s, 1H),
7.88 (d, J = 8.3 Hz, 2H), 7.81 (d, J = 8.5 Hz, 2H), 7.34 (d, J =
8.1 Hz, 2H), 7.27 (d, J = 7.7 Hz, 2H), 2.52 (s, 3H), 2.43 (s, 3H).
13C NMR {1H} NMR (100 MHz, CDCl3) δ 169.3, 149.1, 144.4,
135.5, 131.5, 129.8, 128.5, 128.0, 125.2, 21.7, 14.6. HRMS
1-Isopropoxy-4-(2-phenylallyl)benzene (4ac): yellow oil
(86%, 87 mg), Rf = 0.51 (petroleum ether/dichloromethane =
1
3:1), was synthesized according to General Procedure A; H
NMR (400 MHz, CDCl3) 7.35 (d, J = 7.1 Hz, 2H), 7.23 – 7.12
(m, 3H), 7.03 (d, J = 8.6 Hz, 2H), 6.71 (d, J = 8.6 Hz, 2H), 5.38
(s, 1H), 4.92 (d, J = 1.2 Hz, 1H), 4.50 – 4.31 (m, 1H), 3.68 (s,
2H), 1.23 (d, J = 6.1 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3)
δ 156.6, 147.7, 141.3, 131.7, 130.2, 128.6, 127.7, 126.5, 116.1,
114.59, 70.2, 41.1, 22.4; IR (KBr) ν (cm-1) 2976, 2918, 1611,
1508, 1383, 1242, 1120, 956, 898, 779; HRMS (ESI) calcd for
C18H21O+ [M+H]+ m/z 253.1587, found 253.1590.
+
(ESI) calcd for C15H16NO2S2 [M+H]+ m/z 306.0617, found
306.0624.
5-(2-Phenylallyl)-2,3-dihydrobenzofuran (4ad): yellow oil
(82%, 77 mg), Rf = 0.33 (petroleum ether/dichloromethane =
General Procedure Afor arylation reaction: To a flame-dried
10 mL tube, alkene (1) (0.4 mmol) and bis(4-chlorophenyl)
sulfoxide (2b) (131 mg, 0.48 mmol) were added, and then
dissolved with toluene (2 mL) under nitrogen atmosphere
before cooling down to 0 ºC. Tf2O (81 μL, 0.48 mmol) were
1
3:1), was synthesized according to General Procedure A; H
NMR (400 MHz, CDCl3) δ 7.43 (d, J = 7.3 Hz, 2H), 7.31 – 7.19
(m, 3H), 7.04 (s, 1H), 6.95 (d, J = 8.1 Hz, 1H), 6.68 (d, J = 8.1
Hz, 1H), 5.46 (s, 1H), 5.00 (s, 1H), 4.51 (t, J = 8.7 Hz, 2H), 3.75
(s, 2H), 3.13 (t, J = 8.7 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3) δ 158.8, 147.8, 141.2, 131.7, 128.7, 128.6, 127.7, 127.3,
126.5, 125.7, 114.6, 109.3, 71.5, 41.3, 30.1; IR (KBr) ν (cm-1)
3020, 2894, 1624, 1489, 1384, 1243, 1099, 984, 899, 780, 704;
HRMS (ESI) calcd for C17H17O+ [M+H]+ m/z 237.1274, found
237.1280.
.
added dropwise and kept 15 minutes, then K3PO4 3H2O (266 mg,
1 mmol) and arylboronic (3) (1 mmol) was added. After fully
stirred, warm up to 110 ºC in an oil bath, and kept 12 hours of
reaction at reflux temperature. The solution was quenched by
10 mL water, and then the aqueous phase extracted with CH2Cl2
(10 mL×3). The combined organic phases were dried with
Na2SO4 and concentrated under reduced pressure to give the
crude products. The crude product was then purified by
repeated flash column chromatography and preparative thin
layer chromatography to give pure isolated products. If some
pure products are hard to separate from sulfide, Oxone (0.8
mmol) could add to a solution of crude product in MeOH (10
mL). After the reaction was complete as monitored by TLC, the
solution was quenched by saturated sodium bicarbonate, and
then aqueous phase extracted with CH2Cl2 (10 mL×3). The
5-(2-Phenylallyl)benzo[d][1,3]dioxole (4ae): yellow oil (92%,
92 mg), Rf = 0.43 (petroleum ether/dichloromethane = 3:1), was
1
synthesized according to General Procedure A; H NMR (400
MHz, CDCl3) δ 7.43 – 7.39 (m, 2H), 7.31 – 7.20 (m, 3H), 6.71
– 6.66 (m, 3H) 5.89 (s, 2H), 5.47 (s, 1H), 5.03 (s, 1H), 3.74 (s,
2H); 13C{1H} NMR (100 MHz, CDCl3) δ 147.9, 147.4, 146.2,
141.0, 133.6, 128.6, 127.8, 126.5, 122.2, 114.8, 109.6, 108.5,
101.1, 41.7; IR (KBr) ν (cm-1) 2893, 1621, 1487, 1360, 1244,
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1040, 933, 783, 708; HRMS (ESI) calcd for C16H15O2+ [M+H]+
m/z 239.1067, found 239.1066.
(s, 1H), 4.99 (s, 1H), 3.75 (s, 3H), 3.73 (s, 2H), 2.17 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 156.47, 147.71, 141.31,
131.59, 131.37, 128.54, 127.69, 127.30, 126.69, 126.45, 114.53,
110.14, 55.59, 41.06, 16.55; IR (KBr) ν (cm-1) 2918, 2848, 1663,
1448, 1273, 971, 757, 700; HRMS (ESI) calcd for C17H19O+
[M+H]+ m/z 239.1430, found 239.1430.
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4-(2-Phenylallyl)-1,1'-biphenyl (4af): white solid (65%, 70
mg), Rf = 0.33 (petroleum ether), mp 63-65 ℃, was synthesized
according to General Procedure A; 1H NMR (400 MHz, CDCl3)
δ 7.59 – 7.36 (m, 8H), 7.33 – 7.25 (m, 5H), 7.23 (d, J = 2.8 Hz,
1H), 5.52 (s, 1H), 5.07 (s, 1H), 3.87 (s, 2H); 13C{1H} NMR (100
MHz, CDCl3) δ 147.2, 141.3, 141.1, 139.4, 139.0, 129.7, 129.0,
128.6, 127.9, 127.43, 127.4, 127.3, 126.5, 115.0, 41.6; IR (KBr)
ν (cm-1) 3054, 2974, 1625, 1444, 1265, 907, 751, 702; HRMS
(ESI) calcd for C21H19+ [M+H]+ m/z 271.1481, found 271.1484.
9
2-Chloro-1-methoxy-4-(2-phenylallyl)benzene (4al): yellow
oil (81%, 77 mg), Rf = 0.29 (petroleum ether/dichloromethane
= 3:1), was synthesized according to General Procedure A; 1H
NMR (400 MHz, CDCl3) δ 7.42 – 7.36 (m, 2H), 7.30 – 7.19 (m,
4H), 7.07 – 7.01 (m, 1H), 6.80 (d, J = 8.4 Hz, 1H), 5.48 (s, 1H),
5.02 (s, 1H), 3.83 (s, 3H), 3.74 (s, 2H); 13C{1H} NMR (100
MHz, CDCl3) δ 153.7, 146.9, 140.8, 133.0, 130.87, 128.6, 128.3,
127.9, 126.4, 122.5, 115.1, 112.3, 56.4, 40.8; IR (KBr) ν (cm-1)
2918, 2849, 1625, 1492, 1384, 1275, 1180, 906, 745, 724;
HRMS (ESI) calcd for C16H16ClO+ [M+H]+ m/z 259.0884,
found 259.0887
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1-Phenoxy-4-(2-phenylallyl)benzene (4ag): yellow oil (62%,
71 mg), Rf = 0.58 (petroleum ether/dichloromethane = 3:1), was
1
synthesized according to General Procedure A; H NMR (400
MHz, CDCl3) δ 7.43 (d, J = 7.6 Hz, 2H), 7.33 – 7.22 (m, 5H),
7.17 (d, J = 7.9 Hz, 2H), 7.05 (dd, J = 7.3 Hz, J = 7.3 Hz, 1H),
6.97 (d, J = 7.8 Hz, 2H), 6.91 (d, J = 7.7 Hz, 2H), 5.49 (s, 1H),
5.03 (s, 1H), 3.81 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ
157.8, 155.8, 147.4, 141.1, 134.8, 130.5, 130.0, 128.6, 127.8,
126.5, 123.4, 119.3, 119.0, 114.9, 41.3; IR (KBr) ν (cm-1) 3058,
2919, 1589, 1488, 1239, 871, 777, 704; HRMS (ESI) calcd for
C21H19O+ [M+H]+ m/z 287.1430, found 287.1423.
2-Chloro-4-methoxy-1-(2-phenylallyl)benzene
(4am):
yellow oil (56%, 58 mg), Rf = 0.32 (petroleum ether), was
1
synthesized according to General Procedure A; H NMR (400
MHz, CDCl3) δ 7.45 (d, J = 8.3, 2H), 7.34 – 7.23 (m, 3H), 7.11
(d, J = 8.5 Hz, 1H), 6.93 (d, J = 2.6 Hz, 1H), 6.72 (dd, J = 8.5,
2.6 Hz, 1H), 5.48 (s, 1H), 4.87 (d, J = 1.1 Hz, 1H), 3.85 (s, 2H),
3.77 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 159.0, 146.2,
141.1, 135.1, 131.6, 129.4, 128.7, 127.9, 126.4, 115.0, 114.6,
113.3, 55.8, 38.2; IR (KBr) ν (cm-1) 3020, 2958, 2922, 1626,
1493, 1383, 1028, 899, 777, 700; HRMS (ESI) calcd for
C16H16ClO+ [M+H]+ m/z 259.0884, found 259.0844.
3-(2-Phenylallyl)furan (4ah): yellow oil (35%, 26 mg), Rf =
0.34 (petroleum ether), was synthesized according to General
1
Procedure A; H NMR (400 MHz, CDCl3) δ 7.47 – 7.39 (m,
2H), 7.34 – 7.22 (m, 4H), 6.26 (dd, J = 3.0, 2.0 Hz, 1H), 6.01
(dd, J = 3.0, 0.6 Hz, 1H), 5.48 (s, 1H), 5.10 (d, J = 1.1 Hz, 1H),
3.83 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 153.8, 144.7,
141.6, 140.7, 128.6, 127.9, 126.3, 114.9, 110.7, 107.0, 34.6; IR
(KBr) ν (cm-1) 3057, 2920, 1600, 1504, 1445, 1384, 1010, 899,
788, 701; HRMS (ESI) calcd for C13H13O+ [M+H]+ m/z
185.0961, found 185.0961.
1-Methoxy-4-(2-(p-tolyl)allyl)benzene (4ba): yellow oil (86%,
82 mg), Rf = 0.43 (petroleum ether/dichloromethane = 3:1), was
synthesized according to General Procedure A from 1-methyl-
4-(prop-1-en-2-yl)benzene (1b); 1H NMR (400 MHz, CDCl3) δ
7.35 (d, J = 8.1 Hz, 2H), 7.13 (dd, J = 17.1, 8.3 Hz, 4H), 6.83
(d, J = 8.6 Hz, 2H), 5.46 (s, 1H), 4.98 (d, J = 1.2 Hz, 1H), 3.78
(s, 5H), 2.33 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 158.3,
147.4, 138.2, 137.5, 132.0, 130.2, 129.3, 126.3, 114.1, 113.8,
55.5, 41.1, 21.4; IR (KBr) ν (cm-1) 2931, 1610, 1511, 1392,
1246, 1177, 1036, 902, 831, 778, 755; HRMS (ESI) calcd for
C17H19O+ [M+H]+ m/z 239.1430, found 239.1427.
Prop-2-ene-1,2-diyldibenzene (4ai): yellow oil (43%,33 mg),
Rf = 0.88 (petroleum ether/dichloromethane = 3:1), was
1
synthesized according to General Procedure A; H NMR (400
MHz, CDCl3) δ 7.45 – 7.39 (m, 2H), 7.31 – 7.14 (m, 8H), 5.49
(s, 1H), 5.01 (d, J= 1.2 Hz, 1H), 3.83 (s, 2H); 13C{1H} NMR
(100 MHz, CDCl3) δ 147.27, 141.16, 139.86, 129.27, 128.68,
128.59, 127.79, 126.47, 126.43, 114.92, 41.96; IR (KBr) ν (cm-
1) 3059, 2924, 1625, 1493, 1073, 899, 777, 697; HRMS (ESI)
calcd for C15H15+ [M+H]+ m/z 195.1168, found 195.1172.
1-Bromo-4-(3-(4-methoxyphenyl)prop-1-en-2-yl)benzene
(4da): yellow oil (84%,102 mg), Rf = 0.43 (petroleum
ether/dichloromethane = 3:1), was synthesized according to
General Procedure A from 1-bromo-4-(prop-1-en-2-yl)benzene
9-(2-Phenylallyl)phenanthrene (4aj): white solid (60%, 71
mg), Rf = 0.34 (petroleum ether), mp 160-162 ℃, was
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(1d); H NMR (400 MHz, CDCl3) δ 7.42 (d, J = 8.5 Hz, 2H),
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synthesized according to General Procedure A; H NMR (400
7.30 (d, J = 8.5 Hz, 2H), 7.13 (d, J = 8.5 Hz, 2H), 6.84 (d, J =
8.6 Hz, 2H), 5.48 (s, 1H), 5.08 (d, J = 0.9 Hz, 1H), 3.79 (s, 3H),
3.76 (s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 158.4, 146.6,
140.0, 131.6, 131.4, 130.1, 128.2, 121.7, 115.2, 114.2, 55.5,
41.0; IR (KBr) ν (cm-1) 2920, 1610, 1511, 1247, 1177, 1035,
825; HRMS (ESI) calcd for C16H16BrO+ [M+H]+ m/z 303.0379,
found 303.0387.
MHz, CDCl3) δ 8.70 (d, J = 8.1 Hz, 2H), 8.06 – 8.01 (m, 1H),
7.82 – 7.78 (m, 1H), 7.68 – 7.53 (m, 7H), 7.39 – 7.23 (m, 3H),
5.55 (d, J = 0.8 Hz, 1H), 4.87 (d, J = 1.0 Hz, 1H), 4.28 (s, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 146.3, 141.6, 134.1, 132.2,
131.8, 131.0, 130.2, 128.8, 128.6, 128.2, 128.0, 127.0, 126.6,
126.6, 126.2, 125.3, 123.5, 122.8, 115.4, 39.2; IR (KBr) ν (cm-
1) 2918, 2849, 1625, 1492, 1384, 1275, 1180, 906, 764, 724;
+
HRMS (ESI) calcd for C23H19 [M+H]+ m/z 295.1481, found
1-Fluoro-4-(3-(4-methoxyphenyl)prop-1-en-2-yl)benzene
(4ea): yellow oil (79%, 76 mg), Rf = 0.43 (petroleum
ether/dichloromethane = 3:1), was synthesized according to
295.1477.
1-Methoxy-2-methyl-4-(2-phenylallyl)benzene (4ak): yellow
oil (81%, 77 mg), Rf = 0.43 (petroleum ether/dichloromethane
= 3:1), was synthesized according to General Procedure A; 1H
NMR (400 MHz, CDCl3) δ 7.42 (d, J = 7.9 Hz, 2H), 7.32 – 7.15
(m, 3H), 6.98 (d, J = 6.4 Hz, 2H), 6.70 (d, J = 8.9 Hz, 1H), 5.46
General Procedure
A
from 1-fluoro-4-(prop-1-en-2-
yl)benzene(1e); 1H NMR (400 MHz, CDCl3) δ 7.41 (dd, J = 8.7,
5.5 Hz, 2H), 7.16 (d, J = 8.5 Hz, 2H), 7.02 – 6.96 (m, 2H), 6.85
(d, J = 8.6 Hz, 2H), 5.44 (s, 1H), 5.05 (s, 1H), 3.80 (s, 3H), 3.78
(s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 162.5 (d, J = 246.3
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Hz), 158.4, 146.6, 137.2, 131.5, 130.1, 128.1 (d, J = 7.9 Hz),
NMR (100 MHz, CDCl3) δ 158.3, 138.0, 132.9, 130.2, 123.0,
115.3 (d, J = 21.3 Hz)114.5, 114.1, 55.5, 41.2; 19F NMR (377
MHz, CDCl3) δ -115.09; IR (KBr) ν (cm-1) 2934, 2836, 1601,
1511, 1301, 1247, 1038, 838, 767; HRMS (ESI) calcd for
C16H16FO+ [M+H]+ m/z 243.1180, found 243.1171.
114.0, 55.7, 44.2, 28.4, 25.8, 23.4, 22.9; IR (KBr) ν (cm-1) 2926,
2839, 1610, 1510, 1300, 125, 821, 800; HRMS (ESI) calcd for
C14H19O+ [M+H]+ m/z 203.1430, found 203.1433.
4'-Methoxy-1,2,3,4-tetrahydro-1,1'-biphenyl (4na): yellow
oil (31%,23 mg), Rf = 0.66 (petroleum ether/dichloromethane
= 3:1), was synthesized according to General Procedure A from
1-Methoxy-4-(2-(4-(trifluoromethyl)phenyl)allyl)benzene
(4fa): yellow oil (86%, 100mg), Rf = 0.43 (petroleum
ether/dichloromethane = 3:1), was synthesized according to
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cyclohexene (1n); H NMR (400 MHz, CDCl3) δ 7.14 (d, J =
General
Procedure
A
from
1-(prop-1-en-2-yl)-4-
8.6 Hz, 2H), 6.85 (d, J = 8.7 Hz, 2H), 5.87 (dt, J = 9.7, 6.0, 3.5
Hz, 1H), 5.70 (dd, J = 10.1, 2.1 Hz, 1H), 3.80 (s, 3H), 3.39 –
3.32 (m, 1H), 2.12 – 2.04 (m, 2H), 2.04 – 1.95 (m, 1H), 1.78 –
1.48 (m, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ 158.2, 139.2,
130.9, 129.0, 128.5, 114.0, 55.6, 41.3, 33.1, 25.4, 21.5; IR (KBr)
ν (cm-1) 3017, 2928, 1610, 1511, 1463, 1246, 1177, 1036, 827;
HRMS (ESI) calcd for C13H17O+ [M+H]+ m/z 189.1274, found
189.1269.
1
(trifluoromethyl)benzene (1f); H NMR (400 MHz, CDCl3) δ
7.58 – 7.50 (m, 4H), 7.14 (d, J = 8.4 Hz, 2H), 6.84 (d, J = 8.5
Hz, 2H), 5.55 (s, 1H), 5.16 (s, 1H), 3.80 (s, 2H), 3.79 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3) δ 158.5, 146.6, 144.7, 131.1,
130.1, 129.7 (q, J = 32.3 Hz), 126.8, 125.5 (q, J = 3.6 Hz), 121.9
(q, J = 271.5 Hz), 116.6, 114.2, 55.5, 41.0; 19F NMR (377 MHz,
CDCl3) δ -62.48; IR (KBr) ν (cm-1) 2935, 2836, 1614, 1511,
1404, 1326, 1247, 1119, 847; HRMS (ESI) calcd for
C17H16F3O+ [M+H]+ m/z 293.1148, found 293.1146.
General Procedure B for epoxidation reaction: To a flame-
dried Schlenk tube, alkene (1) (47 mg, 0.4 mmol) and diphenyl
sulfoxide (2a) (97 mg, 0.48 mmol) were added, and then
dissolved with dichloromethane (2 mL) under nitrogen
atmosphere before cooling down to -78 ºC (liquid
nitrogen/ethyl acetate bath). Tf2O (81 μL, 0.48 mmol) were
added dropwise and kept 15 minutes, Then DBU (143 μL,
0.48mmol) and aldehyde (0.6 mmol) was added. After 12 hours
of reaction at -78 ºC and warm up slowly to room temperature.
The solution was quenched by 10 mL water. The aqueous phase
extracted with CH2Cl2 (10 mL×3). The combined organic phase
was dried with Na2SO4 and concentrated under reduced
pressure to give the crude products. Crude 1H NMR was taken
for determination of diastereomeric ratio (see SI page 67-76 for
the characteristic peaks used for dr determination). The crude
product was then purified by repeated flash column
chromatography and preparative thin layer chromatography to
give pure isolated products.
4-(3-(4-Methoxyphenyl)prop-1-en-2-yl)benzonitrile (4ga):
yellow oil (70%, 70 mg), Rf
=
0.12 (petroleum
ether/dichloromethane = 3:1), was synthesized according to
General Procedure A from 4-(prop-1-en-2-yl)benzonitrile (1g);
1H NMR (400 MHz, CDCl3) δ 7.60 – 7.44 (m, 4H), 7.10 (d, J =
8.6 Hz, 2H), 6.82 (d, J = 8.6 Hz, 2H), 5.56 (s, 1H), 5.20 (d, J =
1.0 Hz, 1H), 3.77 (s, 5H); 13C{1H} NMR (100 MHz, CDCl3) δ
158.5, 146.2, 145.6, 132.4, 130.8, 130.0, 127.1, 119.2, 117.5,
114.2, 111.2, 55.5, 40.8; IR (KBr) ν (cm-1) 2955, 2931, 2227,
1606, 1510, 1301, 1246, 1177, 1035, 874, 740; HRMS (ESI)
calcd for C17H16NO+ [M+H]+ m/z 250.1226, found 250.1234.
1-Methoxy-4-(2-methylenebut-3-en-1-yl)benzene
yellow oil (37%, 26 mg), Rf 0.58 (petroleum
(4ka):
=
ether/dichloromethane = 3:1), was synthesized according to
General Procedure A from isoprene (1k); 1H NMR (400 MHz,
CDCl3) δ 7.12 (d, J = 8.6 Hz, 2H), 6.83 (d, J = 8.6 Hz, 2H), 6.43
(dd, J = 17.6, 10.8 Hz, 1H), 5.25 (d, J = 17.6 Hz, 1H), 5.15 (s,
1H), 5.06 (d, J = 10.8 Hz, 1H), 4.90 (s, 1H), 3.79 (s, 3H), 3.50
(s, 2H); 13C{1H} NMR (100 MHz, CDCl3) δ 158.3, 146.0, 138.9,
131.8, 130.1, 118.3, 114.6, 114.1, 55.6, 37.5; IR (KBr) ν (cm-1)
2919, 1610, 1511, 1384, 1247, 1179, 1036; HRMS (ESI) calcd
for C12H15O+ [M+H]+ m/z 175.1117, found 175.1111.
2-Phenyl-3-(1-phenylvinyl)oxirane (trans-) (6aa): yellow oil
(40%, 35mg), Rf = 0.58 (petroleum ether/ethyl acetate = 15:1),
1
was synthesized according to General Procedure B; H NMR
(400 MHz, DMSO- d6) δ 7.56 – 7.30 (m, 10H), 5.63 (s, 1H),
5.43 (s, 1H), 3.96 (s, 1H), 3.87 (s, 1H); 13C{1H} NMR (100
MHz, DMSO- d6) δ 144.6, 138.1, 137.7, 129.6, 129.5, 129.3,
129.2, 126.9, 126.6, 112.6, 62.3, 61.5; IR (KBr) ν (cm-1) 2918,
1629, 1560, 1164, 1025, 878, 806, 668; HRMS (ESI) calcd for
C16H15O+ [M+H]+ m/z 223.1117, found 223.1110.
1-(Cyclopent-1-en-1-ylmethyl)-4-methoxybenzene
yellow oil (44%, 33 mg), Rf 0.48 (petroleum
(4la):
=
ether/dichloromethane = 3:1), was synthesized according to
General Procedure A from methylenecyclopentane (1l); 1H
NMR (400 MHz, CDCl3) δ 7.10 (d, J = 8.5 Hz, 2H), 6.83 (d, J
= 8.5 Hz, 2H), 5.32 (s, 1H), 3.80 (s, 3H), 3.33 (s, 2H), 2.31 (t, J
= 6.1 Hz, 2H), 2.20 (t, J = 7.1 Hz, 2H), 1.90 – 1.80 (m, 2H);
13C{1H} NMR (100 MHz, CDCl3) δ 158.2, 144.6, 132.6, 130.0,
125.4, 114.0, 55.6, 37.4, 35.1, 32.8, 23.9; IR (KBr) ν (cm-1)
3054, 2973, 1609, 1512, 1448, 1384, 1037, 745, 704; HRMS
(ESI) calcd for C13H17O+ [M+H]+ m/z 189.1274, found
189.1269.
2-(4-Fluorophenyl)-3-(1-phenylvinyl)oxirane (trans-) (6ab):
yellow oil (56%, 54 mg), Rf = 0.52 (petroleum ether/ethyl
acetate = 15:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, DMSO- d6) δ 7.56 – 7.48 (m,
4H), 7.45 – 7.35 (m, 3H), 7.28 (m, 2H), 5.63 (s, 1H), 5.41 (s,
1H), 3.98 (s, 1H), 3.91 (d, J = 1.4 Hz, 1H); 13C{1H} NMR (100
MHz, DMSO- d6) δ 163.1 (d, J = 244.3 Hz), 144.5, 138.1, 133.9
(d, J = 2.8 Hz), 129.6, 129.1 (d, J = 7.6 Hz), 129.0, 126.6, 116.4
(d, J = 21.6 Hz), 112.7, 62.3, 60.8; 19F NMR (377 MHz, CDCl3)
δ -113.47; IR (KBr) ν (cm-1) 2918, 2850, 1654, 1560, 1179,
1080, 810, 669; HRMS (ESI) calcd for C16H14FO+ [M+H]+ m/z
241.1023, found 241.1021.
1-(Cyclohex-1-en-1-ylmethyl)-4-methoxybenzene
yellow oil (43%, 38 mg), Rf 0.48 (petroleum
(4ma):
=
ether/dichloromethane = 3:1), was synthesized according to
General Procedure A from methylenecyclohexane(1m); 1H
NMR (400 MHz, CDCl3) δ 7.09 (d, J = 8.5 Hz, 2H), 6.83 (d, J
= 8.6 Hz, 2H), 5.45 (s, 1H), 3.79 (s, 3H), 3.18 (s, 2H), 2.06 –
1.96 (m, 2H), 1.89 – 1.81 (m, 2H), 1.61 – 1.48 (m, 4H); 13C{1H}
2-(4-Bromophenyl)-3-(1-phenylvinyl)oxirane (trans-) (6ac):
yellow oil (50%, 61 mg), Rf = 0.54 (petroleum ether/ethyl
acetate = 15:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.3 Hz,
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2H), 7.43 – 7.31 (m, 5H), 7.24 (d, J = 8.3 Hz, 2H), 5.53 (s, 1H),
HRMS (ESI) calcd for C17H17O+ [M+H]+ m/z 237.1274, found
237.1274.
5.47 (s, 1H), 3.69 (s, 1H), 3.64 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 144.0, 137.9, 136.4, 132.1, 129.0, 128.6, 127.6,
126.4, 122.7, 112.7, 63.0, 61.2; IR (KBr) ν (cm-1) 2981, 2926,
1629, 1594, 1180, 1104, 862, 823, 713, 694; HRMS (ESI) calcd
for C16H14BrO+ [M+H]+ m/z 301.0223, found 301.0221.
2-(3-Methoxyphenyl)-3-(1-phenylvinyl)oxirane
(trans-)
(6ai): yellow oil (31%, 31 mg), Rf = 0.44 (petroleum ether/ethyl
acetate = 15:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, CDCl3) δ 7.43 (d, J = 6.7 Hz,
2H), 7.39 – 7.27 (m, 4H), 6.98 (d, J = 7.6 Hz, 1H), 6.89 (d, J =
6.4 Hz, 2H), 5.52 (s, 1H), 5.47 (s, 1H), 3.83 (s, 3H), 3.71 (s,
1H), 3.68 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 160.4,
144.3, 139.1, 138.0, 130.0, 128.9, 128.5, 126.4, 118.4, 114.5,
112.4, 110.9, 62.8, 61.8, 55.6; IR (KBr) ν (cm-1) 2912, 1685,
1577, 1458, 1383, 1151, 872, 772, 692; HRMS (ESI) calcd for
C17H17O2+ [M+H]+ m/z 253.1223, found 253.1226.
2-(4-Chlorophenyl)-3-(1-phenylvinyl)oxirane (trans-) (6ad) :
yellow oil (53%, 58 mg), Rf = 0.53 (petroleum ether/ethyl
acetate = 15:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, DMSO- d6) δ 7.54 – 7.46 (m,
6H), 7.45 – 7.34 (m, 3H), 5.64 (s, 1H), 5.42 (s, 1H), 3.97 (s, 1H),
3.92 (s, 1H); 13C{1H} NMR (100 MHz, DMSO- d6) δ 144.4,
138.0, 136.8, 133.9, 129.6, 129.5, 129.2, 128.8, 126.6, 112.8,
62.4, 60.7; IR (KBr) ν (cm-1) 2918, 1654, 1560, 1180, 1090, 825,
774, 692; HRMS (ESI) calcd for C16H14ClO+ [M+H]+ m/z
257.0728, found 257.0721.
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55
56
57
58
59
60
2-(4-Nitrophenyl)-3-(1-(p-tolyl)vinyl)oxirane (trans-) (6bg):
white solid (52%, 59 mg), Rf = 0.64 (petroleum ether/ethyl
acetate = 15:1), mp 126-128 ℃, was synthesized according to
General Procedure B; 1H NMR (400 MHz, CDCl3) δ 8.25 (d, J
= 8.6 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 7.29 (d, J = 8.1 Hz, 2H),
7.16 (d, J = 8.0 Hz, 2H), 5.52 (s, 1H), 5.44 (s, 1H), 3.81 (s, 1H),
3.66 (s, 1H), 2.35 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ
148.3, 144.9, 143.4, 138.7, 134.7, 129.7, 126.6, 126.2, 124.3,
112.7, 63.6, 60.5, 21.5; IR (KBr) ν (cm-1) 3075, 2918, 1655,
1560, 1458, 1380, 1345, 1187, 1106, 892, 690; HRMS (ESI)
calcd for C17H16NO3+ [M+H]+ m/z 282.1125, found 282.1127.
2-(1-Phenylvinyl)-3-(4-(trifluoromethyl)phenyl)oxirane
(trans-) (6ae): yellow oil (50%, 58 mg) was synthesized
according to General Procedure B; 1H NMR (400 MHz,
DMSO- d6) δ 7.81 (d, J = 7.1 Hz, 2H), 7.69 (d, J = 7.6 Hz, 2H),
7.51 (d, J = 7.3 Hz, 2H), 7.45 – 7.35 (m, 3H), 5.66 (s, 1H), 5.45
(s, 1H), 4.05 (s, 1H), 4.01 (s, 1H); 13C{1H} NMR (100 MHz,
CDCl3) δ 143.5, 141.1, 137.5, 130.6 (q, J = 32.5 Hz, 1C), 128.6,
128.3, 126.1, 125.9, 125.7 (q, J = 3.6 Hz, 1C), 124.1 (q, J =
272.0 Hz, 1C), 113.0, 62.9, 60.6; 19F NMR (377 MHz, CDCl3)
δ -62.56; IR (KBr) ν (cm-1) 2919, 2849, 1655, 1458, 1166, 1066,
867, 837, 709; HRMS (ESI) calcd for C17H14F3O+ [M+H]+ m/z
291.0991, found 291.0996.
2-(1-(4-Chlorophenyl)vinyl)-3-(4-nitrophenyl)oxirane
(trans-) (6cg): yellow solid (59%, 71 mg), Rf = 0.45 (petroleum
ether/ethyl acetate = 15:1), mp 124-126 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.25 (d, J = 8.6 Hz, 2H), 7.51 (d, J = 8.6 Hz, 2H), 7.32 (s, 4H),
5.55 (s, 1H), 5.51 (s, 1H), 3.80 (d, J = 1.0 Hz, 1H), 3.64 (s, 1H);
13C{1H} NMR (100 MHz, CDCl3) δ 148.3, 144.5, 142.6, 136.0,
134.7, 129.2, 127.8, 126.6, 124.4, 114.5, 63.33, 60.22; IR (KBr)
ν (cm-1) 2918, 2852, 1601, 1518, 1346, 1180, 1094, 893, 853,
4-(3-(1-Phenylvinyl)oxiran-2-yl)benzonitrile (trans-) (6af):
yellow oil (47%, 46 mg), Rf = 0.37 (petroleum ether/ethyl
acetate = 15:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, DMSO- d6) δ 7.92 (d, J = 8.0
Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.50 (d, J = 7.4 Hz, 2H), 7.45
– 7.34 (m, 3H), 5.66 (s, 1H), 5.44 (s, 1H), 4.04 (s, 1H), 4.02 (s,
1H); 13C{1H} NMR (100 MHz, DMSO-d6) δ 144.1, 143.4,
137.9, 133.4, 129.6, 129.2, 127.8, 126.7, 119.6, 113.2, 112.0,
62.8, 60.5; IR (KBr) ν (cm-1) 2918, 2227, 1655, 1560, 1142,
1075, 848, 694; HRMS (ESI) calcd for C17H14NO+ [M+H]+ m/z
248.1070, found 248.1076.
+
745, 693; HRMS (ESI) calcd for C16H13ClNO3 [M+H]+ m/z
302.0578, found 302.0575.
2-(1-(4-Fluorophenyl)vinyl)-3-(4-nitrophenyl)oxirane
(trans-) (6eg): white solid (57%, 65 mg), Rf = 0.57 (petroleum
ether/ethyl acetate = 15:1), , mp 128-130 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.25 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.2 Hz, 2H), 7.40 – 7.31
(m, 2H), 7.09 – 6.97 (m, 2H), 5.50 (s, 1H), 5.48 (s, 1H), 3.80 (s,
1H), 3.63 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ 163.1 (d,
J = 248.0 Hz), 148.3, 144.6, 142.7, 133.7, 128.2 (d, J = 8.1 Hz),
126.6, 124.3, 115.9 (d, J = 21.6 Hz), 114.0, 63.5, 60.2; 19F NMR
(377 MHz, CDCl3) δ -113.32; IR (KBr) ν (cm-1) 2918, 2853,
1655, 1560, 1346, 1160, 894, 873, 751, 694; HRMS (ESI) calcd
for C16H13FNO3+ [M+H]+ m/z 286.0874, found 286.0874.
2-(4-Nitrophenyl)-3-(1-phenylvinyl)oxirane (trans-) (6ag):
yellow solid (63%, 67 mg), Rf = 0.43 (petroleum ether/ethyl
acetate = 15:1), mp 120-122 ℃ was synthesized according to
1
General Procedure B; H NMR (400 MHz, DMSO- d6) δ 8.29
(d, J = 8.5 Hz, 2H), 7.74 (d, J = 8.5 Hz, 2H), 7.54 – 7.32 (m,
5H), 5.67 (s, 1H), 5.46 (s, 1H), 4.12 (s, 1H), 4.03 (s, 1H); 13C{1H}
NMR (100 MHz, DMSO- d6) δ 148.4, 145.5, 144.1, 137.9,
129.6, 129.3, 128.1, 126.7, 124.7, 113.3, 63.0, 60.3; IR (KBr) ν
(cm-1) 2920, 1597, 1521, 1496, 1345, 1180, 1074, 899, 775, 692;
+
HRMS (ESI) calcd for C16H13NO3 [M+H]+ m/z 268.0968,
2-(4-Nitrophenyl)-3-(1-(4-
(trifluoromethyl)phenyl)vinyl)oxirane (trans-) (6fg): yellow
solid (51%, 69 mg), Rf = 0.48 (petroleum ether/ethyl acetate =
15:1), mp 109-112 ℃, was synthesized according to General
Procedure B; 1H NMR (400 MHz, CDCl3) δ 8.26 (d, J = 8.4 Hz,
2H), 7.61 (d, J = 8.1 Hz, 2H), 7.55 – 7.48 (m, 4H), 5.64 (s, 1H),
5.61 (s, 1H), 3.81 (s, 1H), 3.67 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 148.1, 144.0, 142.4, 140.7, 130.4 (q, J = 32.7
Hz), 126.6, 126.3, 125.6 (q, J = 3.8 Hz), 124.0, 124.0 (q, J =
272.1 Hz), 115.8, 62.9, 59.9; 19F NMR (377 MHz, CDCl3) δ -
62.71; IR (KBr) ν (cm-1) 2919, 2860, 1616, 1519, 1197, 1060,
found 268.0969.
2-(1-Phenylvinyl)-3-(p-tolyl)oxirane (trans-) (6ah): yellow
oil (41%, 39 mg), Rf = 0.58 (petroleum ether/ethyl acetate =
1
15:1), was synthesized according to General Procedure B; H
NMR (400 MHz, DMSO- d6) δ 7.49 (d, J = 7.6 Hz, 2H), 7.44 –
7.32 (m, 5H), 7.24 (d, J = 7.8 Hz, 2H), 5.62 (s, 1H), 5.40 (s, 1H),
3.93 (s, 1H), 3.81 (d, J = 1.0 Hz, 1H), 2.35 (s, 3H); 13C{1H}
NMR (100 MHz, DMSO- d6) δ 144.6, 138.7, 138.1, 134.7,
130.0, 129.6, 129.1, 126.9, 126.6, 112.4, 62.2, 61.5, 21.7; IR
(KBr) ν (cm-1) 2917, 2860, 1651, 1550, 1470, 1384, 1072, 810;
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+
849, 742, 690; HRMS (ESI) calcd for C17H13F3NO3 [M+H]+
m/z 336.0842, found 336.0845.
1090, 798, 706; HRMS (ESI) calcd for C13H14NO3+ [M+H]+ m/z
232.0968, found 232.0970.
5
6
7
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2-(4-Nitrophenyl)-3-(1-(4-nitrophenyl)vinyl)oxirane (trans-)
(6hg): yellow solid (65%, 81 mg), Rf = 0.31 (petroleum
ether/ethyl acetate = 20:1), mp 135-138 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.25 (d, J = 8.4 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H), 7.51 (d, J =
8.3 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 5.56 (s, 1H), 5.51 (s, 1H),
3.79 (s, 1H), 3.63 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3) δ
148.3, 144.5, 142.7, 138.1, 137.0, 128.3, 126.6, 124.4, 114.6,
94.5, 63.2, 60.2; IR (KBr) ν (cm-1) 2921, 2851, 1653, 1558,
1345, 1141, 1089, 874, 690; HRMS (ESI) calcd for
C16H13N2O5+ [M+H]+ m/z 313.0819, found 313.0823.
2-(Cyclohex-1-en-1-yl)-3-(4-nitrophenyl)oxirane
(trans-)
(6mg): yellow oil (38%, 37 mg), Rf = 0.58 (petroleum
ether/ethyl acetate = 15:1), was synthesized according to
General Procedure B; 1H NMR (400 MHz, CDCl3) δ 8.21 (d, J
= 8.7 Hz, 2H), 7.45 (d, J = 8.7 Hz, 2H), 5.96 (m, 1H), 3.96 (d,
J = 1.4 Hz, 1H), 3.27 (s, 1H), 2.12 – 1.98 (m, 3H), 1.92 – 1.81
(m, 1H), 1.79 – 1.55 (m, 4H); 13C{1H} NMR (100 MHz, CDCl3)
δ 148.0, 145.8, 133.1, 129.3, 126.5, 124.1, 66.9, 56.7, 25.6, 23.0,
22.7, 22.4; IR (KBr) ν (cm-1) 3010, 2930, 1599, 1520, 1345,
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46
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48
49
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51
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+
1141, 1095, 823, 710, 617; HRMS (ESI) calcd for C14H16NO3
[M+H]+ m/z 246.1125, found 246.1128.
2-(1-(3-Methoxyphenyl)vinyl)-3-(4-nitrophenyl)oxirane
(trans-) (6ig): white solid (24%, 25 mg), Rf = 0.44 (petroleum
ether/ethyl acetate = 15:1), mp 118-120 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.25 (d, J = 8.6 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 7.27 (t, J =
7.9 Hz, 1H), 6.99 – 6.85 (m, 3H), 5.56 (s, 1H), 5.49 (s, 1H),
3.82 (s, 1H), 3.80 (s, 3H), 3.65 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 160.1, 145.2, 144.7, 143.5, 139.1, 130.0, 126.6,
124.3, 118.9, 113.8, 113.8, 112.5, 63.5, 60.5, 55.6; IR (KBr) ν
(cm-1) 2919, 2850, 1655, 1560, 1384, 1343, 1125, 1066, 896,
General Procedure C for aziridination reaction: To a flame-
dried Schlenk tube, alkene (1) (0.4 mmol) and diphenyl
sulfoxide (2a) (97 mg, 0.48 mmol) were added, and then
dissolved with acetonitrile (2 mL) under nitrogen atmosphere
before cooling down to - 43 ºC (liquid nitrogen/acetonitrile
bath). Tf2O (81 μL, 0.48 mmol) were added dropwise and kept
for 15 minutes. Then DBU (143 μL, 0.48mmol) and imine (7)
(0.6 mmol) were added. After 12 hours of reaction at - 43 ºC
and warming up slowly to room temperature, the solution was
quenched by 10 mL water. The aqueous phase extracted with
CH2Cl2 (10 mL×3). The combined organic phase was dried with
Na2SO4 and concentrated under reduced pressure to give the
crude products. Crude 1H NMR was taken for determination of
diastereomeric ratio, Crude 1H NMR was taken for
determination of diastereomer ratio (see SI page 77-81 for the
characteristic peaks used for dr determination). The crude
product was then purified by repeated flash column
chromatography (alumina) and preparative thin layer
chromatography to give pure isolated products.
+
837, 692; HRMS (ESI) calcd for C17H16NO4 [M+H]+ m/z
298.1074, found 298.1078.
2-(1-(2-Chlorophenyl)vinyl)-3-(4-nitrophenyl)oxirane
(trans-) (6jg): yellow solid (38%, 46 mg) , Rf = 0.50 (petroleum
ether/ethyl acetate = 15:1), mp 87-90 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.21 (d, J = 8.7 Hz, 2H), 7.47 (d, J = 8.7 Hz, 2H), 7.41 – 7.34
(m, 1H), 7.30 – 7.26 (m, 3H), 5.70 (s, 1H), 5.36 (s, 1H), 3.79 (d,
J = 1.3 Hz, 1H), 3.54 (d, J = 1.3 Hz, 1H); 13C{1H} NMR (100
MHz, CDCl3) δ 148.2, 144.8, 143.7, 137.3, 133.0, 131.6, 129.9,
129.9, 127.2, 126.6, 124.2, 118.7, 63.8, 60.8; IR (KBr) ν (cm-1)
2919, 2848, 1654, 1560, 1324, 1165, 1066, 867, 708; HRMS
2-Phenyl-3-(1-phenylvinyl)-1-tosylaziridine (8aa): oil (55%,
84 mg), Rf = 0.57 (petroleum ether/ethyl acetate = 5:1), was
1
synthesized according to General Procedure C; H NMR (400
+
(ESI) calcd for C16H13ClNO3 [M+H]+ m/z 302.0578, found
MHz, CDCl3) δ 7.93 (d, J = 8.2 Hz), 7.64 (d, J = 8.3 Hz), 7.47
– 7.14 (m), 5.60 (s, 1H trans), 5.43 (s, 1H trans), 5.40 (s, 1H
cis), 5.25 (s, 1H cis), 4.25 (d, J = 7.2 Hz, 1H cis), 4.19 (d, J =
4.6 Hz, 1H trans), 4.01 – 3.95 (m, 2H trans and cis), 2.44 (s, 3H
cis), 2.38 (s, 3H trans); 13C{1H} NMR (100 MHz, CDCl3) δ
145.1, 144.2, 141.4, 138.6, 138.1, 137.6, 137.4, 135.2, 132.5,
132.2, 130.1, 129.7, 129.2, 129.2, 128.8, 128.7, 128.5, 128.3,
128.2, 128.0, 128.0, 126.5, 126.1, 116.4, 116.3, 51.4, 49.3, 48.4,
47.5, 22.0, 21.9; IR (KBr) ν (cm-1) 3021, 1597, 1447, 1328,
1162, 1089, 901, 752, 698; HRMS (ESI) calcd for C23H22NO2S+
[M+H]+ m/z 376.1366, found 376.1374.
302.0575.
2-(Buta-1,3-dien-2-yl)-3-(4-nitrophenyl)oxirane
(trans-)
(6kg): white solid (45%, 39 mg), Rf = 0.48 (petroleum
ether/ethyl acetate = 15:1), mp 60-63 ℃, was synthesized
according to General Procedure B; 1H NMR (400 MHz, CDCl3)
δ 8.24 (d, J = 8.5 Hz, 2H), 7.50 (d, J = 8.5 Hz, 2H), 6.45 (dd, J
= 17.9, 11.1 Hz, 1H), 5.36 (s, 1H), 5.24 (d, J = 17.7 Hz, 1H),
5.23 (s, 1H), 5.15 (d, J = 11.0 Hz, 1H), 3.76 (s, 1H), 3.55 (s,
1H); 13C{1H} NMR (100 MHz, CDCl3) δ 148.3, 144.9, 141.7,
135.9, 126.6, 124.3, 115.8, 115.4, 61.8, 59.8; IR (KBr) ν (cm-1)
3085, 2963, 2851, 1648, 1571, 1347, 1179, 1095, 908, 851, 695;
2-(4-Chlorophenyl)-3-(1-phenylvinyl)-1-tosylaziridine
(8ab): oil (50%, 82 mg), Rf = 0.51 (petroleum ether/ethyl
acetate = 5:1), was synthesized according to General Procedure
C; 1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz), 7.66 (d,
J = 8.2 Hz), 7.45 – 7.08 (m), 5.58 (s, 1H trans), 5.42 (s), 5.39
(s, 1H trans), 5.22 (s, 1H cis), 4.20 (d, J = 7.2 Hz, 1H cis), 4.16
(d, J = 4.6 Hz, 1H trans), 3.97 (d, J = 7.3 Hz, 1H cis), 3.92 (d,
J = 4.7 Hz, 1H trans), 2.45 (s, 3H cis), 2.40 (s, 3H trans); 13C{1H}
NMR (100 MHz, CDCl3) δ 144.5, 141.3, 138.5, 137.3, 135.2,
131.1, 130.6, 130.2, 129.8, 129.4, 129.1, 128.9, 128.8, 128.6,
128.5, 128.4, 127.9, 126.5, 125.9, 116.5, 116.4, 50.7, 49.4, 48.5,
46.6, 22.0, 21.9; IR (KBr) ν (cm-1): 2921, 1700, 1598, 1494,
1329, 1160, 1092, 908, 812, 780; HRMS (ESI) calcd for
C23H21ClNO2S+ [M+H]+ m/z 410.0976, found 410.0979
+
HRMS (ESI) calcd for C12H12NO3 [M+H]+ m/z 218.0812,
found 218.0813.
2-(Cyclopent-1-en-1-yl)-3-(4-nitrophenyl)oxirane (trans-)
(6lg): yellow oil (31%, 29 mg), Rf = 0.40 (petroleum ether/ethyl
acetate = 20:1), was synthesized according to General
Procedure B; 1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 8.6 Hz,
2H), 7.45 (d, J = 8.6 Hz, 2H), 6.00 (t, J = 3.2 Hz 1H), 3.99 (d,
J = 1.3 Hz, 1H), 3.54 (s, 1H), 2.48 – 2.33 (m, 3H), 2.32 – 2.19
(m, 1H), 2.02 – 1.88 (m, 2H); 13C{1H} NMR (100 MHz, CDCl3)
δ 148.1, 145.6, 140.1, 133.1, 126.5, 124.1, 62.2, 57.8, 33.2, 30.7,
23.4; IR (KBr) ν (cm-1) 2962, 2824, 1603, 1520, 1384, 1141,
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2-(4-Bromophenyl)-3-(1-phenylvinyl)-1-tosylaziridine (8ac):
1328, 1161, 1089, 911, 812, 776, 707; HRMS (ESI) calcd for
oil (45%, 81 mg), Rf = 0.57 (petroleum ether/ethyl acetate = 5:1)
C24H24NO2S+ [M+H]+ m/z 390.1522 , found 390.1514.
1
was synthesized according to General Procedure C; H NMR
2-([1,1'-Biphenyl]-4-yl)-3-(1-phenylvinyl)-1-tosylaziridine
(8ag): oil (58%, 105 mg) was synthesized according to General
Procedure C; 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.2 Hz),
7.67 (d, J = 8.2 Hz), 7.62 – 7.17 (m), 5.60 (s, 1H trans), 5.46 –
5.40 (m, 2H trans and cis), 5.29 (s, 1H cis), 4.29 (d, J = 7.2 Hz,
1H cis), 4.25 (d, J = 4.7 Hz, 1H trans), 4.02 – 3.97 (m, 2H trans
and cis), 2.45 (s, 3H cis), 2.40 (s, 3H trans); 13C{1H} NMR (100
MHz, CDCl3) δ 145.1, 144.3, 142.1, 141.1, 141.1, 140.8, 140.7,
138.6, 137.7, 137.4, 131.4, 130.2, 129.7, 129.2, 129.0, 128.9,
128.7, 128.5, 128.5, 128.4, 128.0, 127.9, 127.7, 127.5, 127.5,
127.3, 126.9, 126.5, 126.1, 116.5, 116.2, 51.4, 49.2, 48.5, 47.3,
22.0, 21.9; IR (KBr) ν (cm-1): 3030, 2922, 1598, 1328, 1162,
1089, 912, 812, 763, 696; HRMS (ESI) calcd for C29H26NO2S+
[M+H]+ m/z 452.1679, found 452.1674.
(400 MHz, CDCl3) δ 7.91 (d, J = 8.2 Hz), 7.65 (d, J = 8.2 Hz),
7.48 (d, J = 8.4 Hz), 7.44 – 7.15 (m), 7.05 (d, J = 8.3 Hz), 5.58
(s, 1H trans), 5.42 (s, 1H cis), 5.39 (s, 1H trans), 5.22 (s, 1H
cis), 4.18 (d, J = 7.2 Hz, 1H cis), 4.14 (d, J = 4.5 Hz, 1H trans),
3.97 (d, J = 7.2 Hz, 1H cis), 3.91 (d, J = 4.7 Hz, 1H trans), 2.44
(s, 3H cis), 2.40 (s, 3H trans); 13C{1H} NMR (100 MHz, CDCl3)
δ 144.5, 141.2, 138.5, 137.2, 132.0, 131.6, 131.4, 130.8, 130.3,
129.8, 129.7, 128.9, 128.8, 128.6, 128.5, 128.3, 127.9, 126.4,
125.9, 123.4, 116.5, 116.4, 50.6, 49.4, 48.4, 46.7, 22.0, 21.9; IR
(KBr) ν (cm-1): 3057, 2923, 1597, 1492, 1397, 1328, 1161, 911,
813, 707; HRMS (ESI) calcd for C23H21BrNO2S+ [M+H]+ m/z
454.0471, found 454.0477.
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2-(4-Fluorophenyl)-3-(1-phenylvinyl)-1-tosylaziridine (8ad):
oil (41%, 65 mg), Rf = 0.57 (petroleum ether/ethyl acetate =
1
2-(Naphthalen-2-yl)-3-(1-phenylvinyl)-1-tosylaziridine
(8ah): oil (56%, 96 mg), Rf = 0.46 (petroleum ether/ethyl
acetate = 5:1), was synthesized according to General Procedure
5:1), was synthesized according to General Procedure C; H
NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz), 7.65 (d, J = 8.2
Hz), 7.48 – 7.12 (m), 7.05 (t, J = 8.6 Hz), 6.86 (t, J = 8.7 Hz),
5.57 (s, 1H trans), 5.41 (s, 1H cis), 5.38 (s, 1H trans), 5.21 (s,
1H cis), 4.22 (d, J = 7.2 Hz, 1H cis), 4.18 (d, J = 4.7 Hz, 1H
trans), 3.97 – 3.91 (m, 2H trans and cis), 2.46 (s, 3H cis), 2.41
(s, 3H trans); 13C{1H} NMR (100 MHz, CDCl3) δ 164.6, 162.1,
145.2, 144.4, 141.4, 138.5, 137.9, 137.6, 137.4, 131.2, 131.1,
130.2, 129.8, 129.6, 128.9, 128.7, 128.6, 128.5, 128.4, 128.2,
127.9, 126.5, 125.98, 116.5, 116.2, 116.0, 115.8, 115.4, 115.2,
51.0, 49.2, 48.5, 46.6, 22.0, 21.9; 19F NMR (376 MHz, CDCl3)
δ -112.34, -113.96; IR (KBr) ν (cm-1): 2920, 1599, 1513, 1446,
1328, 1162, 1088, 913, 816, 707; HRMS (ESI) calcd for
C23H21FNO2S+ [M+H]+ m/z 394.1272, found 394.1278.
1
C; H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.3 Hz), 7.87 –
7.17 (m), 7.13 (d, J = 8.1 Hz), 5.64 (s), 5.50 (s, 1H trans), 5.39
(s, 1H trans), 5.31 (s, 1H cis), 4.40 (d, J = 7.2 Hz), 4.30 (d, J =
4.4 Hz, 1H trans), 4.15 (d, J = 4.7 Hz, 1H trans), 4.04 (d, J =
7.2 Hz, 1H cis), 2.44 (s, 3H cis), 2.35 (s, 3H trans); 13C{1H}
NMR (100 MHz, CDCl3) δ 144.3, 141.5, 138.7, 137.3, 133.7,
133.3, 130.2, 129.9, 129.7, 129.1, 128.9, 128.7, 128.6, 128.5,
128.4, 128.3, 128.1, 128.0, 127.5, 127.0, 126.8, 126.5, 126.5,
126.4, 126.2, 126.1, 125.6, 116.5, 116.4, 51.6, 49.5, 48.6, 47.7,
22.0, 21.9; IR (KBr) ν (cm-1): 3054, 2916, 1598, 1446, 1328,
1162, 1088, 912, 815, 707; HRMS (ESI) calcd for C27H24NO2S+
[M+H]+ m/z 426.1522, found 426.1529.
2-(1-Phenylvinyl)-1-tosyl-3-(4-
2-(4-Methoxyphenyl)-3-(1-phenylvinyl)-1-tosylaziridine
(8ai): oil (29%, 47 mg), Rf = 0.66 (petroleum ether/ethyl acetate
= 3:1), was synthesized according to General Procedure C; 1H
NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.3 Hz), 7.65 (d, J = 8.3
Hz), 7.47 – 7.19 (m), 7.12 (d, J = 8.7 Hz), 6.89 (d, J = 8.7 Hz),
6.73 – 6.68 (m), 5.54 (s, 1H cis), 5.42 (s, 1H trans), 5.36 (s, 1H
cis), 5.25 (s, 1H trans), 4.24 (d, J = 4.8 Hz, 1H trans), 4.20 (d,
J = 7.2 Hz, 1H cis), 3.92 (d, J = 7.2 Hz, 1H cis), 3.89 (d, J = 4.7
Hz, 1H trans), 3.82 (s, 3H cis), 3.71 (s, 3H trans), 2.44 (s, 3H
trans), 2.40 (s, 3H cis); 13C{1H} NMR (100 MHz, CDCl3) δ
160.4, 159.7, 145.0, 144.2, 141.9, 138.5, 138.2, 137.8, 137.6,
135.3, 130.9, 130.1, 129.7, 129.2, 128.9, 128.7, 128.5, 128.3,
127.9, 126.4, 126.1, 124.3, 123.8, 116.3, 115.6, 114.2, 113.7,
55.6, 55.5, 52.3, 48.5, 48.4, 47.2; IR (KBr) ν (cm-1): 2921, 1598,
1496, 1328, 1161, 1090, 912, 803, 707; HRMS (ESI) calcd for
C24H24NO3S+ [M+H]+ m/z 406.1471, found 406.1478.
(trifluoromethyl)phenyl)aziridine (8ae): oil (45%, 80 mg), Rf
= 0.60 (petroleum ether/ethyl acetate = 5:1), was synthesized
according to General Procedure C; 1H NMR (400 MHz, CDCl3)
δ 7.93 (d, J = 7.9 Hz), 7.66 (d, J = 7.9 Hz), 7.58 (m), 7.45 – 7.17
(m), 5.63 (s, 1H trans), 5.44 (s, 1H trans), 5.42 (s, 1H cis), 5.23
(s, 1H cis), 4.27 (d, J = 7.3 Hz, 1H cis), 4.15 (d, J = 4.6 Hz, 1H
trans), 4.06 – 3.98 (m, 2H trans and cis), 2.46 (s, 3H cis), 2.40
(s, 3H trans); 13C{1H} NMR (100 MHz, CDCl3) δ 145.4, 144.6,
140.9, 138.5, 137.7, 137.3, 137.1, 137.0, 134.9, 131.1, 130.3,
129.8, 129.4, 128.9, 128.8, 128.6, 128.6, 128.4, 128.4, 128.0,
126.5, 125.9, 125.9, 125.8, 125.8, 125.8, 116.8, 116.6, 50.1,
50.0, 48.5, 46.6, 22.1, 21.9; 19F NMR (376 MHz, CDCl3) δ -
62.64, -62.69; IR (KBr) ν (cm-1) 2921, 1597, 1494, 1328, 1162,
1088, 928, 802; HRMS (ESI) calcd for C24H21F3NO2S+ [M+H]+
m/z 444.1240, found 444.1248
2-(1-Phenylvinyl)-3-(p-tolyl)-1-tosylaziridine (8af): oil (57%,
89 mg), Rf = 0.46 (petroleum ether/ethyl acetate = 5:1), was
2-(4-(Methylthio)phenyl)-3-(1-phenylvinyl)-1-tosylaziridine
(8aj): oil (39%, 66 mg), Rf = 0.67 (petroleum ether/ethyl acetate
= 3:1), was synthesized according to General Procedure C; 1H
NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz), 7.65 (d, J = 8.2
Hz), 7.45 – 7.16 (m), 7.08 (m), 5.56 (s, 1H trans), 5.42 (s), 5.38
(s, 1H trans), 5.25 (s), 4.22 – 4.17 (m, 2H trans and cis), 3.95
(d, J = 7.2 Hz, 1H cis), 3.90 (d, J = 4.8 Hz, 1H trans), 2.48 (s,
3H trans), 2.44 (s, 3H cis), 2.40 (s, 3H trans), 2.38 (s, 3H cis);
13C{1H} NMR (100 MHz, CDCl3) δ 145.1, 144.3, 141.5, 140.1,
138.7, 138.5, 138.0, 137.6, 137.4, 135.1, 130.2, 129.8, 129.7,
129.0, 128.9, 128.7, 128.5, 128.5, 128.4, 128.3, 127.91, 126.4,
126.4, 126.1, 126.0, 116.4, 116.0, 51.6, 48.9, 48.5, 47.2, 22.0,
21.9, 15.8, 15.8; IR (KBr) ν (cm-1): 2973, 2933, 1606, 1445,
1
synthesized according to General Procedure C; H NMR (400
MHz, CDCl3) δ 7.95 – 7.89 (m), 7.65 (d, J = 8.1 Hz), 7.47 –
7.12 (m), 7.08 (d, J = 7.9 Hz), 6.97 (d, J = 7.9 Hz), 5.55 (s, 1H
trans), 5.41 (s, 1H cis), 5.37 (s, 1H trans), 5.26 (s, 1H cis), 4.27
– 4.18 (m, 2H trans and cis), 3.97 – 3.88 (m, 2H trans and cis),
2.43 (s, 3H cis), 2.39 (s, 3H trans), 2.36 (s, 3H trans), 2.22 (s,
3H cis); 13C{1H} NMR (100 MHz, CDCl3) δ 145.0, 144.2, 141.7,
139.1, 138.6, 138.2, 138.0, 137.7, 137.6, 135.2, 130.1, 129.7,
129.5, 129.3, 129.2, 129.2, 129.0, 128.8, 128.7, 128.5, 128.3,
127.9, 126.4, 126.1, 116.3, 115.9, 52.0, 48.8, 48.4, 47.5, 22.0,
21.9, 21.6, 21.4; IR (KBr) ν (cm-1): 3030, 2922, 1598, 1446,
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1380, 1334, 1046, 881, 748, 691; HRMS (ESI) calcd for
Resumed. Angew. Chem. Int. Ed. 2011, 50, 6824–6827. (d)
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ASSOCIATED CONTENT
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catalysed asymmetric allylic arylation of racemic halides with
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S.; Gualtierotti, J.-B.; Goh, S. S.; Feringa, B. L.
Enantioselective Synthesis of Di- and Tri-Arylated All-Carbon
Quaternary Stereocenters via Copper-Catalyzed Allylic
Arylations with Organolithium Compounds. ACS Catalysis.
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Supporting Information
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Optimization of reaction conditions, copies of spectra
AUTHOR INFORMATION
Corresponding Author
* Email: lipf@mail.buct.edu.cn
Author Contributions
All authors have given approval to the final version of the
manuscript.
ACKNOWLEDGMENT
This research was supported in part by National Natural Science
Foundation of China (21402005) and the Fundamental Research
Funds for the Central Universities (XK-1802-6, 12060093063).
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17. For our group’s research on activited sulfoxide mediated
reaction with alkenes and alkynes, see: (a) Hu, G.; Xu, J.; Li, P.
Sulfur Mediated Allylic C–H Alkylation of Tri- and
Disubstituted Olefins. Org. Lett. 2014, 16, 6036–6039. (b)
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19. Cabré, A.; Sciortino, G.; Ujaque, G.; Verdaguer, X.; Lledós,
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