N-heterocyclic carbene-palladium(II)-1-methylimidazole complex catalyzed α-arylation reactions of tetralones with aryl chlorides and further transformation of the products

Article abstract of DOI:10.1039/c5ob01203a

NHC-Pd(II)-Im complex 1 has proven to be an efficient catalyst in the reaction between tetralones 2 and aryl chlorides 3, giving the α-arylated tetralones 4 in good to high yields. In addition, if the above reaction mixture was exposed to air at room temp

Full text of DOI:10.1039/c5ob01203a

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N-Heterocyclic
Carbene-Palladium(II)-1-Methylimidazole
DOI: 10.1039/C5OB01203A
View Article Online
Complex Catalyzed α-Arylation Reactions of Tetralones with
Aryl Chlorides and Further Transformation of the Products
Hui-Ying Yin, Xia-Li Lin, Shu-Wan Li and Li-Xiong Shao*
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
NHC-Pd(II)-Im complex 1 have proven an efficient catalyst in the reaction between tetralones 2
and aryl chlorides 3, giving the α-arylated tetralones 4 in good to high yields. In addition, if the
10 above reaction mixture was exposed to air at room temperature for another 3 h, the normal α-
arylated products 4 can be fully oxidized to 2-aryl-2’-hydroxytetralones 6 in good yields in a one-
pot procedure. Furthermore, if the reaction mixture containing the oxidized products 6 was treated
with TsOH/toluene solution under reflux for 19 h, the final aromatized products, 2-aryl-
naphthalen-1-ols 5 can be achieved in acceptable to moderate yields. All reactions can tolerate
15 various substituents on the tetralones 2 and aryl chlorides 3, thus giving efficient method for the α-
arylation of tetralones and further transformation of the products, and also enriching the
applications of NHC-Pd(II) complexes in organic synthesis.
mixture of the α-arylation reaction was exposed to air at room
temperature, the α-arylated products can be fully oxidized to
2-aryl-2’-hydroxytetralones 6 in a one-pot procedure. Herein,
we report these results in detail.
Introduction
During the past years, N-heterocyclic carbene (NHC)-metal
20 complexes, which are usually air-, moisture- and thermal-
stable, have proven efficient catalysts in the α-arylation of
ketones and have become strong competitors to phosphine-
metal complexes in such transformation.1,2 In 2011, we
developed a well-defined N-heterocyclic carbene-Pd(II)-1-
25 methylimidazole [NHC-Pd(II)-Im] complex 1,3 and found it to
be an efficient catalyst in the C-C and C-N coupling reactions
using the inactive, while easily available and cost-superior
aryl chlorides as the electrophiles.4 For example, we recently
reported a novel two-component, three-molecule reaction
30 between 2,3-dihydroinden-1-ones and aryl chlorides in the
presence of NHC-Pd(II)-Im complex 1, and proposed the
plausible reaction mechanism.4k Prompted by these results, we
thus turned our interest to the reactions of their analogs,
tetralones, with aryl chlorides catalyzed by NHC-Pd(II)-Im
35 complex 1, because 2-aryltetralones are also important
precursors for the synthesis of benzophenanthridine bases and
their derivatives.5 However, to the best of our knowledge,
compared to the abundant papers on the palladium-catalyzed
α-aryaltion of other carbonyl containing compounds, very less
40 attention was paid on the transition metal-catalyzed α-
arylation of tetralones,6 and only handful examples were
reported on the palladium-catalyzed such reaction using aryl
chlorides as the arylating agents with very lower yields,6b,6d,6g
implying that great challenge still kept in such tranformation.
45 Pleasantly, after careful investigations, we found that NHC-
Pd(II)-Im complex 1 can efficiently catalyze the α-arylation
of tetralones 2 with aryl chlorides 3. In addition, successively
treatment the above reaction mixture by air-oxidation, and
acid-catalyzed aromatization, 2-aryl-naphthalen-1-ols 5 can be
50 achieved in moderate to good yields. Furthermore, if the
55
Results and discussion
The optimization procedure was carried out using tetralone 2a
(1.0 mmol) and chlorobenzene 3a (1.2 mmol) as the substrates,
NHC-Pd(II)-Im complex 1 (1.0 mol%) as the catalyst at 110
60 oC for 12 h to evaluate various solvents (2.0 mL) and bases
(2.0 equiv). Some representative results are shown in Table 1.
Initially, toluene was chosen as the solvent to test bases. In
the presence of KOtBu, the desired α-arylated 4a was
obtained in 68% yield, along with 2-phenylnaphtnalen-1-ol 5a
65 in 14% yield (Table 1, entry 1). In the presence of other bases
such as NaOtBu and KOH, very low yields of products 4a and
5a were observed at the same time (Table 1, entries 2 and 3).
In addition, using some other bases such as LiOtBu, K2CO3,
.
.
Na2CO3, Cs2CO3, NaOH, Na3PO4 12H2O and K3PO4 3H2O, no
70 reaction occurred. Next, using KOtBu as the base, a variety of
solvents was subsequently tested. Using dioxane as the
solvent instead of toluene, 4a was obtained in 76% yield along
with 5a in 18% yield (Table 1, entry 4). In other solvents such
as CH3CN, DMF and DMSO, no reaction occurred. Finally,
75 the best result for the sole α-arylation reaction was achieved
when the amount of KOtBu increased to 3.0 equiv (Table 1,
entry 5).
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Page 2 of 10
Table 1. Representative results of NHC-Pd(II)-Im complex 1
catalyzed reaction of tetralone 2a with chlorobenzene 3a.
View Article Online
DOI: 10.1039/C5OB01203A
Cl
O
O
NHC-Pd(II)-Im 1
(1.0 mol%)
+
base, solvent
110 oC, 12 h
3a
4a
+
2a
OH
Pri
Pri
Pri
Cl
N
N
N
N
Pd
Cl
5a
Pri
NHC-Pd(II)-Im 1
Yield (%)b
5a
Entrya
Base (equiv)
KOtBu (2.0)
Solvent
4a
1
2
3
4
5
toluene
toluene
toluene
dioxane
dioxane
68
14
NaOtBu (2.0)
KOH (2.0)
<5
25
76
85
7
12
18
KOtBu (2.0)
KOtBu (3.0)
25 In addition, a variety of tetralones 2 and aryl chlorides 3 were
further investigated under the optimal conditions to test the
scope and limitations of this reaction. The results are
illustrated in Table 3. As can be seen from Table 3, all
reactions examined gave the desired α-arylated tetralones 4 in
30 moderate to high yields. It seems that electron-rich, -poor, and
sterically-hindered substituents on both substrates did not
affect the reactions significantly. For example, electron-rich
group such as 6-MeO and 7-MeO and electron-poor 7-F
substituted tetralones 2b, 2c and 2d worked well with various
35 aryl chlorides 3 to give products 4i-4w in moderate to high
yields (Table 3). Sterically-hindered 2-methylphenyl chloride
3b was also suitable substrate to give the corresponding
products 4j, 4q and 4u in good yields (Table 3, entries 3, 11,
15).
a All reactions were carried out using 1a (1.0 mmol), 2a (1.2 mmol),
base, 1 (1.0 mol%) in solvent (2.0 mL) at 110 oC for 12 h.
b Isolated yields.
With the optimal conditions for the α-arylation reaction
established, the reactions between tetralone 2a and a variety
of aryl chlorides 3 were then first investigated (Table 2). As
can be seen from Table 2, substituents on aryl chlorides 3
affected the reactions to some extent. For example, for the
moderately electron-rich methyl substituted aryl chlorides 3b-
d, the reactions can be carried out at 110 oC to afford
5
10 satisfactory yields (Table 2, entries 1-3). While for the
reaction involving electron-rich 3-methoxyphenyl chloride 3e,
only moderate yields can be obtained even if the reaction
temperature increased to 130 oC (Table 2, entries 4 and 5). For
the reaction involving 4-methoxyphenyl chloride 3f, high
15 yield can still be achieved when the reaction temperature was
40
o
elevated to 130 C (Table 2, entries 6 and 7). For the reactions
involving electron-poor fluorine substituted aryl chlorides 3g
and 3h, moderate yields were obtained under identical
conditions (Table 2, entries 8 and 9). Sterically hindered 2-
20 methylphenyl chloride 3b was the most suitable substrate to
give product 4b in the highest yield (Table 2, entry 1).
2
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can be actually fully oxidized by air in a one-pot procedure.
View Article Online
However, comparable yield of product 5DaOwI:a1s0.o10b3s9e/rCv5eOdBi0n12th0i3sA
30 case, implying that the aromatization of the oxidized product
6a to product 5a cannot easily take place under such
conditions (Scheme 1).
35
It was known that 2-aryl-2’-hydroxytetralone can aromatize to
2-aryl-naphthalen-1-ols in the presence of p-toluenesulfonic
acid (TsOH).7 Therefore, we then turned our interest to the
cascade reaction involving three steps such as NHC-Pd(II)-Im
40 complex 1 catalyzed α-arylation of tetralones 2 with aryl
chlorides 3, air-oxidation in
a one-pot procedure and
aromatization for the final formation of 2-aryl-naphthalen-1-
ols 5. The results are shown in Table 4. As can be seen from
Table 4, after the normal α-arylation reaction under suitable
45 conditions was finished, the reaction mixture was cooled to
room temperature and exposed to air for another 3 h. Then the
mixture was dropped to the solution of TsOH in toluene (the
toluene solution was pre-refluxed for 2 h), and the mixture
As can be seen from Table 1, entry 4, the normal α-arylated
product 4a and 2-phenyl-naphthalen-1-ol 5a can be obtained
in very high total yields at the same time in the presence of 2
equiv KOtBu in dioxane. In our initial assumption, 2-phenyl-
naphthalen-1-ol 5a can derive from the normal α-arylated
product 4a via aromatization under suitable conditions. As
stated above, the NHC-Pd(II)-Im complex 1 catalyzed α-
5
o
was then stirred at 110 C for 19 h, finally giving the desired
50 2-aryl-naphthalen-1-ols 5 in acceptable to moderate yields.
Similarly, for all reactions shown in Table 4, it seems that
electron-rich, -neutral and -poor substituents on both
substrates did not affect the reactions significantly.
10 arylation reaction between a variety of tetralones 2 and aryl
chlorides 3 can be successfully achieved to give the desired α-
arylated products 4 in moderate to good yields under the
optimal conditions (Tables 1-3). Encouraged by these
successful results, we then turned our interest to the sole
15 formation of products 5. Considering that in our preliminary
investigation on the NHC-Pd(II)-Im complex 1-catalyzed α-
arylation of oxindoles with aryl chlorides, the normal α-
arylated products can be efficiently oxidized under air at room
temperature in
a
one-pot procedure.4j Therefore, we
20 hypothesized that the normal α-arylated products 4 would also
be oxidized under air, and then the oxidized products would
then aromatize to give the final 2-aryl-naphthalen-1-ols 5.
Control experiment showed that when the model reaction
shown in Table 1, entry 4 was finished and then the mixture
25 was stirred at room temperature under air for 3 h, the oxidized
product 6a can be obtained in 64% yield without any detection
of product 4a, implying that the normal α-arylated product 4a
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Page 4 of 10
View Article Online
DOI: 10.1039/C5OB01203A
15
In addition, it was found that for the reaction between
tetralone 2a and heteroaryl chloride such as 3-chloropyridine
3i, 2-(pyridine-3-yl)-naphthalen-1-ol 5o can be obtained in 68%
yield as the sole product under the normal α-arylation
20 conditions after SiO2-column chromatography, probably
implying that the normal α-arylated product deriving from
such reaction can be easily oxidized under air during the
work-up process and the oxidized intermediate can proceed
aromatization when SiO2-column chromatography was carried
25 out (Scheme 2).
It was worthy of noting here that in the above cascade
reaction, sterically-hindered substituents on the aryl chlorides
affected the reactions significantly. For example, for the
reactions between tetralones 2 and 2-methylphenyl chloride
3b, the sequential α-arylation and air-oxidation reaction can
take place smoothly to give the desired oxidized products 6 in
good to high yields (Table 5). However, when the mixture was
10 treated with TsOH/toluene solution, the reactions became
disordered and no obvious product can be isolated by SiO2
column chromatography.
5
Finally, the reaction between 6,7,8,9-tetrahydro-5H-
30 benzo[7]annulen-5-one 2e with 4-methylphenyl chloride 3d
was also tested under identical conditions. As can be seen
from Scheme 3, the reaction also worked well to give the
desired α-arylated product 4x in 84% yield.
35
Conclusions
In conclusion, well-defined NHC-Pd(II)-Im complex
1
showed efficient catalytic activity toward the α-arylation of
40 tetralones 2 with easily available and cheaper aryl chlorides 3,
4
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giving the desired α-arylated products 4 in good to high yields.
After the α-arylation reaction was completed, the normal α-
arylated products 4 can be further fully oxidized to the α-
purified
by
flash
column
chromatography
(eluent:
View Article Online
petroleum/ethyl acetate = 180/1) to give pure products 5.
DOI: 10.1039/C5OB01203A
arylated-oxidized products, the 2-aryl-2’-hydroxytetralones 6, 55 General Procedure for the Formation of α-Arylated-Oxidized
5
in good yields in a one-pot procedure under air at room
temperature. Furthermore, if the mixture of the above α-
arylation-oxidation reaction was treated with TsOH/toluene
solution under reflux, the final aromatized products, 2-aryl-
naphthalen-1-ols 5, can be achieved in acceptable to moderate
Products 6. Under N2 atmosphere, NHC-Pd(II)-Im complex 1
(1.0 mol%), KOtBu (3.0 equiv), dioxane (1.0 mL), tetralones 2
(0.5 mmol) and 2-methylphenyl chloride 3b (0.6 mmol) were
successively added into a Schlenk reaction tube. The mixture was
60 stirred vigorously at the specified temperature for 12 h. Then it
was cooled to room temperature, exposed to air and stirred at
room temperature for another 3 h. Then the solvent was removed
under reduced pressure and the residue was purified by flash
column chromatography (eluent: petroleum/ethyl acetate = 50/1)
65 to give pure products 6.
10 yields. Various substituents on both substrates of tetralones 2
and aryl chlorides 3 are tolerated in all the above reactions,
thus providing facile and versatile methodologies for the
synthesis α-arylated tetralones, 2-aryl-2’-hydroxytetralones
and 2-aryl-naphthalen-1-ols and also enriching the
15 applications of NHC-Pd(II)-Im complex in organic synthesis.
Compound 4a2f: white solid (188.7 mg, 85%). 1H NMR (300
MHz, CDCl3, TMS) δ 2.40-2.48 (m, 2H), 3.00-3.13 (m, 2H), 3.81
(t, J = 7.5 Hz, 1H), 7.19 (d, J = 7.8 Hz, 2H), 7.25-7.37 (m, 5H),
7.51 (t, J = 7.5 Hz, 1H), 8.10 (d, J = 7.8 Hz, 1H). 13C NMR (125
70 MHz, CDCl3) δ 28.7, 31.2, 54.3, 126.7, 126.9, 127.8, 128.4,
128.5, 128.7, 132.9, 133.4, 139.7, 144.0, 198.1.
Experimental
General Remarks. Melting points are uncorrected. NMR spectra
were recorded at 500 (for 1H NMR) or 125 MHz (for 13C NMR),
1
respectively. H NMR and 13C NMR spectra recorded in CDCl3
1
Compound 4b2f: yellow liquid (114.5 mg, 97%). H NMR (500
20 solutions were referenced to TMS (0.00 ppm) and the residual
solvent peak (77.0 ppm), respectively. J-values are in Hz.
Organic solvents used were dried by standard methods. The mass
analyzer type for the high resolution mass spectra is quadrupole.
Other commercially obtained reagents were used without further
25 purification. Flash column chromatography was performed on
silica gel.
MHz, CDCl3, TMS) δ 2.30 (s, 3H), 2.33 (dd, J = 8.5, 4.5 Hz, 1H),
2.42 (ddd, J = 23.5, 11.5, 4.5 Hz, 1H), 3.03 (dt, J = 10.2, 4.5 Hz,
75 1H), 3.12 (ddd, J = 16.0, 11.5, 4.5 Hz, 1H), 3.96 (dd, J = 11.5, 4.5
Hz, 1H), 7.03-7.05 (m, 1H), 7.12-7.20 (m, 3H), 7.27 (d, J = 7.5
Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.48 (td, J = 7.5, 1.5 Hz, 1H),
8.09 (d, J = 8.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 19.8,
29.3, 30.2, 51.4, 126.0, 126.6, 126.8, 127.5, 127.6, 128.7, 130.4,
80 132.9, 133.3, 136.4, 138.5, 144.0, 197.9.
General Procedure for the Formation of α-Arylated Products
4. Under N2 atmosphere, NHC-Pd(II)-Im complex 1 (1.0 mol%),
KOtBu (3.0 equiv), dioxane (1.0 mL), tetralones 2 (0.5 mmol)
30 and aryl chlorides 3 (0.6 mmol) were successively added into a
Schlenk reaction tube. The mixture was stirred vigorously at the
specified temperature for 12 h. Then it was cooled to room
temperature, diluted with ethyl acetate (10 mL) and acidified by
saturated aqueous NH4Cl to adjust the PH value to 7.0. Then the
35 organic layer was separated and dried over anhydrous Na2SO4,
filtered, concentrated under reduced pressure and purified by
flash column chromatography (eluent: petroleum/ethyl acetate =
150/1) to give pure products 4.
o
1
Compound 4c: white solid (94.4 mg, 80%); mp: 60-62 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.33 (s, 3H), 2.38-2.47 (m, 2H),
3.01-3.13 (m, 2H), 3.75 (dd, J = 10.0, 6.0 Hz, 1H), 6.98 (d, J =
7.5 Hz, 1H), 7.00 (s, 1H), 7.07 (d, J = 7.5 Hz, 1H), 7.20-7.24 (m,
85 1H), 7.27 (d, J = 7.5 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.49 (td, J
= 7.5, 1.0 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H). 13C NMR (125 MHz,
CDCl3) δ 21.4, 28.8, 31.2, 54.4, 125.4, 126.7, 127.7, 127.8, 128.4,
128.7, 129.2, 132.9, 133.3, 138.0, 139.7, 144.1, 198.2. MS (ESI):
259 [M+Na]+; HRMS (ESI) calcd. for C17H16NaO [M+Na]+:
90 259.1099; found: 259.1085. IR (KBr) ν 3054, 2928, 2399, 1680,
1600, 1491, 1457, 1431, 1318, 1222, 1152, 906, 778, 740, 718,
700 cm-1.
General Procedure for the Formation of α-Arylated-
40 Oxidized-Aromatized Products 5. Under N2 atmosphere, NHC-
Pd(II)-Im complex 1 (1.0 mol%), KOtBu (3.0 equiv), dioxane
(1.0 mL), tetralones 2 (0.5 mmol) and aryl chlorides 3 (0.6 mmol)
were successively added into a Schlenk reaction tube. The
mixture was stirred vigorously at the specified temperature for 12
45 h. Then it was cooled to room temperature, exposed to air and
stirred at room temperature for another 3 h. Then the mixture was
dropped to a toluene solution of TsOH, which was pre-refluxed
for 2 h, and the obtained mixture was refluxed for another 19 h.
After the mixture was cooled to room temperature, it was diluted
50 with ethyl acetate and washed by saturated aqueous NaHCO3 (5
mL). The organic layer was separated and dried over anhydrous
Na2SO4, filtered, concentrated under reduced pressure and
Compound 4d5d: white solid (98.0 mg, 83%). 1H NMR (500 MHz,
CDCl3, TMS) δ 2.33 (s, 3H), 2.39-2.43 (m, 2H), 3.01-3.13 (m,
95 2H), 3.76 (dd, J = 9.5, 6.0 Hz, 1H), 7.08 (d, J = 8.0 Hz, 2H), 7.14
(d, J = 8.0 Hz, 2H), 7.26 (d, J = 7.5 Hz, 1H), 7.32 (t, J = 7.5 Hz,
1H), 7.49 (td, J = 7.5, 1.5 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H). 13C
NMR (125 MHz, CDCl3) δ 21.0, 28.7, 31.1, 54.0, 126.7, 127.8,
128.2, 128.7, 129.2, 132.9, 133.3, 136.4, 136.6, 144.0, 198.3.
o
1
100 Compound 4e: white solid (93.3 mg, 74%); mp: 85-87 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.41-2.45 (m, 2H), 3.02-3.14
(m, 2H), 3.76-3.79 (m, 4H), 6.74 (s, 1H), 6.78 (d, J = 7.5 Hz, 1H),
6.81 (dd, J = 7.5, 2.5 Hz, 1H), 7.25 (d, J = 7.0 Hz, 1H), 7.28 (d, J
= 7.0 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.50 (td, J = 7.5, 1.0 Hz,
105 1H), 8.09 (d, J = 7.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
28.7, 31.1, 54.4, 55.2, 112.2, 114.5, 120.8, 126.8, 127.8, 128.7,
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Page 6 of 10
129.5, 132.9, 133.4, 141.2, 144.0, 159.7, 198.0. MS (ESI): 275
[M+Na]+; HRMS (ESI) calcd. for C17H16NaO2 [M+Na]+:
275.1048; found: 275.1021. IR (KBr) ν 3067, 2935, 1680, 1600,
J = 2.5 Hz, 1H), 6.85 (dd, J = 9.0, 2.5 Hz, 1H), 6.97-7.00 (m, 2H),
7.07 (d, J = 7.5 Hz, 1H), 7.21 (t, J = 7.5 Hz,D1OHI:),108..100739(/dC,5JO=B091.2003A
Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 21.4, 29.0, 31.3, 54.0,
View Article Online
1491, 1461, 1424, 1355, 1322, 1295, 1033, 964, 920, 861, 821, 60 55.4, 112.5, 113.2, 125.4, 126.6, 127.6, 128.3, 129.1, 130.2,
5
786, 750, 697 cm-1.
138.0, 140.0, 146.5, 163.6, 197.1. MS (ESI): 289 [M+Na]+;
HRMS (ESI) calcd. for C18H18NaO2 [M+Na]+: 289.1204; found:
289.1175. IR (KBr) ν 2941, 1673, 1600, 1487, 1448, 1335, 1242,
Compound 4f8: white solid (114.7 mg, 91%). 1H NMR (500 MHz,
CDCl3, TMS) δ 2.39-2.43 (m, 2H), 3.02-3.15 (m, 2H), 3.75 (t, J =
8.0 Hz,1H), 3.80 (s, 3H), 6.88 (d, J = 8.5 Hz, 2H), 7.11 (d, J = 8.5
1222, 1099, 1010, 920, 909, 901, 872, 851, 834, 786, 703 cm-1.
Hz, 2H), 7.27 (d, J = 7.5 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.49 65 Compound 4l: yellow solid (93.1 mg, 70%); mp: 54-56 C. 1H
o
10 (td, J = 7.5, 1.5 Hz, 1H), 8.09 (d, J = 7.5 Hz, 1H). 13C NMR (125
MHz, CDCl3) δ 28.8, 31.2, 53.6, 55.3, 114.0, 126.7, 127.8, 128.7,
129.3, 131.8, 132.9, 133.4, 144.0, 158.5, 198.4.
NMR (500 MHz, CDCl3, TMS) δ 2.32 (s, 3H), 2.36 (dd, J = 12.5,
7.5 Hz, 2H), 2.94-3.06 (m, 2H), 3.70 (t, J = 7.5 Hz, 1H), 3.84 (s,
3H), 6.70 (d, J = 2.5 Hz, 1H), 6.83 (dd, J = 9.0, 2.5 Hz, 1H), 7.06
(d, J = 8.0 Hz, 2H), 7.12 (d, J = 8.0 Hz, 2H), 8.06 (d, J = 9.0 Hz,
o
1
Compound 4g: white solid (92.4 mg, 77%); mp: 79-81 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.39-2.43 (m, 2H), 3.04 (dt, J = 70 1H). 13C NMR (125 MHz, CDCl3) δ 21.0, 28.9, 31.2, 53.5, 55.3,
15 16.5, 4.5 Hz, 1H), 3.12 (dt, J = 16.5, 7.5 Hz, 1H), 3.79 (t, J = 8.0
Hz, 1H), 6.90 (dt, J = 10.0, 2.0 Hz, 1H), 6.94-6.98 (m, 2H), 7.27-
7.35 (m, 3H), 7.50 (td, J = 7.5, 1.5 Hz, 1H), 8.09 (d, J = 7.5 Hz,
112.5, 113.2, 126.5, 128.2, 129.1, 130.2, 136.2, 136.9, 146.5,
163.5, 197.0. MS (ESI): 289 [M+Na]+; HRMS (ESI) calcd. for
C18H18NaO2 [M+Na]+: 289.1204; found: 289.1203. IR (KBr) ν
2935, 2849, 1686, 1597, 1514, 1494, 1451, 1341, 1245, 1103,
1H). 13C NMR (125 MHz, CDCl3) δ 28.7, 31.0, 54.1 (d, JC-F
=
1.50 Hz), 113.8 (d, JC-F = 20.875 Hz), 115.4 (d, JC-F = 21.625 Hz), 75 1030, 897, 816, 785, 753 cm-1.
1
20 124.2 (d, JC-F = 2.75 Hz), 126.8, 128.0, 128.8, 129.9 (d, JC-F
8.25 Hz), 132.6, 133.6, 142.1 (d, JC-F = 7.25 Hz), 143.9, 162.9 (d,
C-F = 244.125 Hz), 197.4. MS (ESI): 263 [M+Na]+; HRMS (ESI)
calcd. for C16H13FNaO [M+Na]+: 263.0848; found: 263.0839. IR
=
Compound 4m: yellow solid (115.7 mg, 82%); mp: 77-79 oC. H
NMR (500 MHz, CDCl3, TMS) δ 2.35-2.40 (m, 2H), 2.94-3.05
(m, 2H), 3.72 (t, J = 7.5 Hz, 1H), 3.76 (s, 3H), 3.84 (s, 3H), 6.70
(d, J = 2.5 Hz, 1H), 6.73 (d, J = 2.0 Hz, 1H), 6.76 (d, J = 7.5 Hz,
J
(KBr) ν 3050, 2941, 2895, 1676, 1587, 1484, 1444, 1305, 1265, 80 1H), 6.79 (dd, J = 7.5, 2.0 Hz, 1H), 6.84 (dd, J = 9.0, 2.5 Hz, 1H),
25 1222, 1139, 1007, 962, 919, 884, 864, 823, 780, 741, 715, 685
7.23 (t, J = 7.5 Hz, 1H), 8.06 (d, J = 9.0 Hz, 1H). 13C NMR (125
MHz, CDCl3) δ 28.8, 31.1, 53.9, 55.0, 55.3, 112.0, 112.5, 113.2,
114.4, 120.7,126.4, 129.3, 130.1, 141.5, 146.5, 159.6, 163.6,
196.7. MS (ESI): 305 [M+Na]+; HRMS (ESI) calcd. for
cm-1.
Compound 4h5d: white solid (96.0 mg, 80%). 1H NMR (500
MHz, CDCl3, TMS) δ 2.39-2.43 (m, 2H), 3.05 (dt, J = 16.5, 4.5
Hz, 1H), 3.14 (dt, J = 16.5, 7.5 Hz, 1H), 3.78 (t, J = 8.5 Hz, 1H), 85 C18H18NaO3 [M+Na]+: 305.1154; found: 305.1143. IR (KBr) ν
30 7.03 (t, J = 8.5 Hz, 2H), 7.16 (dd, J = 8.5, 5.0 Hz, 2H), 7.29 (d, J
= 8.0 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.51 (td, J = 7.5, 1.0 Hz,
1H), 8.09 (d, J = 8.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
28.9, 31.3, 53.7, 115.4 (d, JC-F = 21.25 Hz), 126.8, 127.8, 128.8,
2941, 2835, 1680, 1571, 1487, 1451, 1434, 1358, 1278, 1259,
1161, 1103, 1036, 1020, 917, 896, 877, 859, 826, 793, 775, 751,
695 cm-1.
Compound 4n9: white solid (114.3 mg, 81%). 1H NMR (500
129.9 (d, JC-F = 7.875 Hz), 132.7, 133.5, 135.4 (d, JC-F = 3.25 Hz), 90 MHz, CDCl3, TMS) δ 2.34-2.39 (m, 2H), 2.95-3.08 (m, 2H), 3.71
35 143.9, 161.8 (d, JC-F = 241.375 Hz), 197.9.
(dd, J = 8.5, 6.5 Hz, 1H), 3.79 (s, 3H), 3.86 (s, 3H), 6.71 (d, J =
2.5 Hz, 1H), 6.83-6.88 (m, 3H), 7.10 (d, J = 8.5 Hz, 2H), 8.06 (d,
J = 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 29.0, 31.3, 53.1,
55.2, 55.4, 112.5, 113.2, 113.9, 126.5, 129.3, 130.2, 132.0, 146.5,
Compound 4i5d: white solid (92.0 mg, 73%). 1H NMR (500 MHz,
CDCl3, TMS) δ 2.38-2.42 (m, 2H), 2.96-3.09 (m, 2H), 3.76 (t, J =
7.5 Hz, 1H), 3.87 (s, 3H), 6.72 (d, J = 2.5 Hz, 1H), 6.86 (dd, J =
8.5, 2.5 Hz, 1H), 7.18 (d, J = 7.5 Hz, 2H), 7.26 (t, J = 7.5 Hz, 1H), 95 158.4, 163.5, 197.2.
40 7.33 (t, J = 7.5 Hz, 2H), 8.08 (d, J = 8.5 Hz, 1H). 13C NMR (125
MHz, CDCl3) δ 29.0, 31.3, 54.0, 55.4, 112.6, 113.3, 126.6, 126.8,
128.4, 128.5, 130.3, 140.0, 146.5, 163.6, 197.0.
Compound 4o10: white solid (104.0 mg, 77%). 1H NMR (500
MHz, CDCl3, TMS) δ 2.35-2.41 (m, 2H), 2.99 (dt, J = 17.0, 4.5
Hz, 1H), 3.05-3.11 (m, 1H), 3.74 (dd, J = 10.0, 6.0 Hz, 1H), 3.87
(s, 3H), 6.73 (d, J = 2.5 Hz, 1H), 6.86 (dd, J = 8.5, 2.5 Hz, 1H),
o
1
Compound 4j: yellow solid (113.1 mg, 85%); mp: 72-74 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.26-2.40 (m, 5H), 2.97 (dt, J = 100 7.02 (t, J = 9.0 Hz, 2H), 7.15 (dd, J = 8.5, 5.0 Hz, 2H), 8.06 (d, J
45 16.5, 4.5 Hz, 1H), 3.03-3.10 (m, 1H), 3.83 (s, 3H), 3.92 (dd, J =
11.5, 5.0 Hz, 1H), 6.72 (d, J = 2.5 Hz, 1H), 6.83 (dd, J = 9.0, 2.5
Hz, 1H), 7.02-7.04 (m, 1H), 7.10-7.20 (m, 3H), 8.06 (d, J = 9.0
Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 19.7, 29.5, 30.3, 51.0,
= 8.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 29.1, 31.4, 53.3,
55.5, 112.6, 113.3, 115.3 (d, JC-F = 21.25), 126.4, 129.9 (d, JC-F
7.875), 130.3, 135.7 (d, JC-F = 3.625), 146.2, 161.8 (d, JC-F
243.375), 163.7, 196.7.
=
=
o
1
55.3, 112.4, 113.1, 125.9, 126.59, 126.62, 127.5, 130.0, 130.4, 105 Compound 4p: yellow solid (92.0 mg, 73%); mp: 74-75 C. H
50 136.3, 138.8, 146.4, 163.5, 196.7. MS (ESI): 289 [M+Na]+;
HRMS (ESI) calcd. for C18H18NaO2 [M+Na]+: 289.1204; found:
289.1187. IR (KBr) ν 2935, 2822, 1680, 1603, 1491, 1454, 1355,
1249, 1152, 1096, 1020, 897, 852, 834, 799, 750, 731 cm-1.
NMR (500 MHz, CDCl3, TMS) δ 2.37-2.42 (m, 2H), 2.93-3.05
(m, 2H), 3.77 (t, J = 8.0 Hz, 1H), 3.83 (s, 3H), 7.08 (dd, J = 8.5,
3.0 Hz, 1H), 7.17-7.19 (m, 3H), 7.24-7.27 (m, 1H), 7.33 (t, J =
7.5 Hz, 2H), 7.58 (d, J = 3.0 Hz, 1H). 13C NMR (125 MHz,
Compound 4k: yellow solid (110.4 mg, 83%); mp: 84-86 oC. 1H 110 CDCl3) δ 27.8, 31.4, 54.1, 55.4, 109.7, 121.7, 126.8, 128.4, 128.5,
55 NMR (500 MHz, CDCl3, TMS) δ 2.33 (s, 3H), 2.37-2.41 (m, 2H),
2.95-3.07 (m, 2H), 3.71 (t, J = 7.5 Hz, 1H), 3.86 (s, 3H), 6.72 (d,
129.9, 133.6, 136.6, 139.8, 158.4, 198.1. MS (ESI): 253 [M+H]+;
HRMS (ESI) calcd. for C17H17O2 [M+H]+: 253.1223; found:
6
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Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 10
Organic & Biomolecular Chemistry
253.1223. IR (KBr) ν 2941, 2841, 1673, 1607, 1497, 1457, 1418,
1690, 1610, 1494, 1418, 1355, 1312, 1259, 1232, 1149, 1106,
1053, 1027, 891, 834, 809, 796, 750, 733, D7O13I: c10m.1-10.3V9ie/wC5AOrtiBcl0e1O2n0li3nAe
Compound 4v: yellow solid (102.9 mg, 81%); mp: 91-93 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.34 (s, 3H), 2.38-2.43 (m, 2H),
1348, 1331, 1272, 1242, 1202, 1196, 1172, 1023, 881, 872, 844,
813, 775, 753, 730, 695 cm-1.
o
1
o
Compound 4q: yellow solid (117.1 mg, 88%); mp: 84-86 C. 1H
5
NMR (500 MHz, CDCl3, TMS) δ 2.28-2.43 (m, 5H), 2.97 (dt, J = 60 2.98-3.09 (m, 2H), 3.74 (t, J = 8.0 Hz, 1H), 7.06 (d, J = 8.0 Hz,
16.5, 4.5 Hz, 1H), 3.02-3.08 (m, 1H), 3.82 (s, 3H), 3.94 (dd, J =
12.0, 4.5 Hz, 1H), 7.03-7.05 (m, 1H), 7.08 (dd, J = 8.5, 3.0 Hz,
1H), 7.12-7.16 (m, 2H), 7.17-7.21 (m, 2H), 7.58 (d, J = 3.0 Hz,
1H). 13C NMR (125 MHz, CDCl3) δ 19.8, 28.4, 30.5, 51.2, 55.4,
2H), 7.15 (d, J = 8.0 Hz, 2H), 7.19 (td, J = 8.5, 3.0 Hz, 1H), 7.25
(dd, J = 8.5, 5.0 Hz, 1H), 7.74 (dd, J = 8.5, 3.0 Hz, 1H). 13C
NMR (125 MHz, CDCl3) δ 21.0, 28.0, 31.1, 53.6, 113.6 (d, JC-F
21.625 Hz), 120.7 (d, JC-F = 22.125 Hz), 128.2, 129.3, 130.5 (d,
JC-F = 7.00 Hz), 134.4 (d, JC-F = 6.00 Hz), 136.2, 136.6, 139.7 (d,
=
10 109.6, 121.6, 126.0, 126.8, 127.5, 129.9, 130.4, 133.8, 136.4,
136.6, 138.6, 158.4, 197.9. MS (ESI): 289 [M+Na]+; HRMS
(ESI) calcd. for C18H18NaO2 [M+Na]+: 289.1204; found:
289.1177. IR (KBr) ν 3021, 2935, 1912, 1683, 1610, 1570, 1497,
1348, 1331, 1242, 1166, 1033, 877, 833, 816, 798, 763, 750, 728,
15 713 cm-1.
65
JC-F = 2.875 Hz), 161.6 (d, JC-F = 244.875 Hz), 197.3 (d, JC-F
=
1.5 Hz). MS (ESI): 277 [M+Na]+; HRMS (ESI) calcd. for
C17H15FNaO [M+Na]+: 277.1005; found: 277.0981. IR (KBr) ν
2948, 2862, 1683, 1607, 1583, 1517, 1487, 1424, 1358, 1318,
70 1259, 1232, 1156, 902, 889, 848, 818, 786, 731, 705 cm-1.
1
o
Compound 4r: yellow liquid (102.5 mg, 77%). H NMR (500
Compound 4w: white solid (113.4 mg, 84%); mp: 102-104 C.
1H NMR (500 MHz, CDCl3, TMS) δ 2.37-2.42 (m, 2H), 2.99-
3.10 (m, 2H), 3.73 (t, J = 8.0 Hz, 1H), 3.80 (s, 3H), 6.89 (d, J =
9.0 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 7.20 (td, J = 8.0, 3.0 Hz,
MHz, CDCl3, TMS) δ 2.33 (s, 3H), 2.35-2.39 (m, 2H), 2.92-3.04
(m, 2H), 3.73 (t, J = 7.5 Hz, 1H), 3.82 (s, 3H), 7.06-7.08 (m, 3H),
7.13-7.18 (m, 3H), 7.57 (d, J = 3.0 Hz, 1H). 13C NMR (125 MHz,
20 CDCl3) δ 21.0, 27.8, 31.4, 53.7, 55.4, 109.7, 121.6, 128.2, 129.1, 75 1H), 7.25-7.27 (m, 1H), 7.74 (dd, J = 9.0, 3.0 Hz, 1H). 13C NMR
129.9, 133.6, 136.4, 136.6, 136.7, 158.4, 198.2. MS (ESI): 289
[M+Na]+; HRMS (ESI) calcd. for C18H18NaO2 [M+Na]+:
289.1204; found: 289.1174. IR (KBr) ν 3007, 2928, 2829, 2365,
2051, 1898, 1683, 1604, 1567, 1487, 1418, 1328, 1265, 1239,
25 1172, 1113, 1033, 960, 881, 816, 786, 755, 730, 705 cm-1.
Compound 4s11: yellow solid (129.8 mg, 92%). 1H NMR (500
MHz, CDCl3, TMS) δ 2.33-2.38 (m, 2H), 2.92-3.04 (m, 2H), 3.71
(t, J = 8.0 Hz, 1H), 3.78 (s, 3H), 3.82 (s, 3H), 6.87 (d, J = 9.0 Hz,
2H), 7.07 (dd, J = 8.5, 2.5 Hz, 1H), 7.09 (d, J = 9.0 Hz, 2H), 7.17
(125 MHz, CDCl3) δ 28.1, 31.2, 53.2, 55.3, 113.6 (d, JC-F = 21.75
Hz), 114.1, 120.7 (d, JC-F = 22.125 Hz), 129.3, 130.6 (d, JC-F
=
7.00 Hz), 131.3, 134.4 (d, JC-F = 6.00 Hz), 139.7 (d, JC-F = 3.00
Hz), 158.6, 161.6 (d, JC-F = 244.75 Hz), 197.4 (d, JC-F = 1.625
80 Hz). MS (ESI): 293 [M+Na]+; HRMS (ESI) calcd. for
C17H15FNaO2 [M+Na]+: 293.0954; found: 293.0935. IR (KBr) ν
2921, 1686, 1607, 1517, 1491, 1421, 1355, 1315, 1255, 1176,
1149, 1106, 1027, 902, 882, 831, 788, 735, 703 cm-1.
1
Compound 4x: yellow liquid (105.1 mg, 84%). H NMR (500
30 (d, J = 8.5 Hz, 1H), 7.56 (d, J = 2.5 Hz, 1H). 13C NMR (125 MHz, 85 MHz, CDCl3, TMS) δ 1.79-1.87 (m, 1H), 2.06-2.19 (m, 3H), 2.33
CDCl3) δ 27.7, 31.3, 53.2, 55.1, 55.3, 109.7, 113.8, 121.5, 129.2,
(s, 3H), 2.96-3.00 (m, 1H), 3.06-3.11 (m, 1H), 4.02 (dd, J = 11.0,
5.0 Hz, 1H), 7.13-7.17 (m, 4H), 7.23 (d, J = 7.5 Hz, 1H), 7.28 (t,
J = 7.5 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.61 (d, J = 7.5 Hz, 1H).
13C NMR (125 MHz, CDCl3) δ 21.0, 25.4, 31.2, 32.9, 55.4, 126.5,
129.8, 131.7, 133.5, 136.5, 158.3, 158.4, 198.2.
o
1
Compound 4t: white solid (87.6 mg, 73%); mp: 88-90 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.41-2.45 (m, 2H), 2.99-3.11
35 (m, 2H), 3.78 (t, J = 7.5 Hz, 1H), 7.17-7.22 (m, 3H), 7.25-7.29 (m, 90 128.4, 128.5, 129.0, 129.6, 131.4, 136.4, 137.2, 140.0, 141.1,
2H), 7.34 (t, J = 7.5 Hz, 2H), 7.75 (dd, J = 9.0, 2.5 Hz, 1H). 13C
NMR (125 MHz, CDCl3) δ 28.0, 31.1, 54.0, 113.5 (d, JC-F
21.75 Hz), 120.7 (d, JC-F = 22.125 Hz), 127.0, 128.3, 128.6, 130.6
(d, JC-F = 7.00 Hz), 134.4 (d, JC-F = 6.00 Hz), 139.3, 139.7 (d, JC-F
40 = 2.875 Hz), 161.6 (d, JC-F = 244.875 Hz), 197.1 (d, JC-F = 1.5 95 Compound 5a12: yellow solid (78.1 mg, 71%). 1H NMR (500
205.8. MS (ESI): 273 [M+Na]+; HRMS (ESI) calcd. for
C18H18NaO [M+Na]+: 273.1251; found: 273.1250. IR (KBr) ν
3014, 2935, 2861, 1686, 1597, 1514, 1444, 1269, 1199, 1023,
980, 957, 813, 794, 761, 735 cm-1.
=
Hz). MS (ESI): 263 [M+Na]+; HRMS (ESI) calcd. for
C16H13FNaO [M+Na]+: 263.0848; found: 263.0835. IR (KBr) ν
3067, 2921, 2855, 1673, 1610, 1494, 1457, 1424, 1358, 1318,
1259, 1235, 1149, 1083, 962, 909, 886, 834, 811, 776, 750, 727
MHz, CDCl3, TMS) δ 5.85 (s, 1H), 7.36 (d, J = 8.0 Hz, 1H), 7.43
(td, J = 9.0, 4.5 Hz, 1H), 7.48-7.52 (m, 3H), 7.54 (d, J = 4.5 Hz,
4H), 7.81-7.83 (m, 1H), 8.29-8.30 (m, 1H). 13C NMR (125 MHz,
CDCl3) δ 120.2, 121.2, 122.4, 124.3, 125.5, 126.5, 127.5, 127.6,
100 127.9, 129.3, 129.6, 134.2, 137.4, 147.7.
45 cm-1.
1
1
Compound 4u: colorless liquid (99.1 mg, 78%). H NMR (500
Compound 5b13: brown liquid (70.2 mg, 60%). H NMR (500
MHz, CDCl3, TMS) δ 2.30 (s, 3H), 2.32-2.44 (m, 2H), 3.00-3.12
(m, 2H), 3.94 (dd, J = 12.0, 5.0 Hz, 1H), 7.02-7.04 (m, 1H), 7.13-
7.20 (m, 4H), 7.26 (dd, J = 8.5, 5.0 Hz, 1H), 7.73 (dd, J = 9.0, 2.5
MHz, CDCl3, TMS) δ 2.43 (s, 3H), 5.91 (s, 1H), 7.23 (d, J = 8.5
Hz, 1H), 7.32-7.35 (m, 3H), 7.42 (t, J = 7.5 Hz, 1H), 7.47 (d, J =
9.0 Hz, 1H), 7.48-7.51 (m, 2H), 7.80-7.82 (m, 1H), 8.28-8.29 (m,
50 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 19.8, 28.6, 30.3, 51.1, 105 1H). 13C NMR (125 MHz, CDCl3) δ 21.5, 120.1, 121.3, 122.4,
113.4 (d, JC-F = 21.75 Hz), 120.6 (d, JC-F = 22.125 Hz), 126.1,
126.9, 127.4, 130.5, 130.6, 134.5 (d, JC-F = 6.00 Hz), 136.4, 138.2,
139.7, 161.5 (d, JC-F = 244.75 Hz), 196.9. MS (ESI): 277
[M+Na]+; HRMS (ESI) calcd. for C17H15FNaO [M+Na]+:
124.2, 125.5, 126.2, 126.4, 127.4, 127.5, 128.6, 129.5, 130.0,
134.1, 137.3, 139.4, 147.7.
o
Compound 5c: yellow solid (67.9 mg, 58%); mp: 74-76 C. 1H
NMR (500 MHz, CDCl3, TMS) δ 2.43 (s, 3H), 5.86 (s, 1H), 7.34
55 277.1005; found: 277.0977. IR (neat) ν 3054, 3014, 2935, 2868, 110 (d, J = 8.5 Hz, 3H), 7.42 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 8.0 Hz,
1H), 7.49-7.52 (m, 2H), 7.80-7.82 (m, 1H), 8.27-8.29 (m, 1H).
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7

Organic & Biomolecular Chemistry
Page 8 of 10
13C NMR (125 MHz, CDCl3) δ 21.2, 120.1, 121.2, 122.4, 124.2,
125.4, 126.3, 127.4, 127.6, 129.2, 130.3, 134.0, 134.2, 137.7,
147.7. MS (ESI): 235 [M+H]+; HRMS (ESI) calcd. for C17H15O
281.1169. IR (KBr) ν 3451, 1630, 1603, 1577, 1511, 1431, 1375,
View Article Online
1282, 1242, 1199, 1020, 942, 877, 852, 831,D7O66I:,1701.1503c9m/C-15.OB01203A
o
1
Compound 5i: white solid (75.6 mg, 54%); mp: 125-127 C. H
[M+H]+: 235.1123; found: 235.1109. IR (KBr) ν 3524, 3338, 60 NMR (500 MHz, CDCl3, TMS) δ 3.86 (s, 3H), 3.92 (s, 3H), 5.76
5
1573, 1501, 1461, 1381, 1295, 1245, 1179, 1099, 1046, 1017,
(s, 1H), 7.04 (d, J = 9.0 Hz, 2H), 7.11 (d, J = 2.5 Hz, 1H), 7.15
(dd, J = 9.0, 2.5 Hz, 1H), 7.28 (d, J = 8.5 Hz, 1H), 7.34 (d, J =
8.5 Hz, 1H), 7.43 (d, J = 9.0 Hz, 2H), 8.18 (d, J = 9.0 Hz, 1H).
13C NMR (125 MHz, CDCl3) δ 55.26, 55.35, 105.7, 115.0, 117.9,
879, 806, 746, 723 cm-1.
Compound 5d: brown solid (72.5 mg, 58%); mp: 103-105 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 3.88 (s, 3H), 5.81 (s, 1H), 7.07
(d, J = 9.0 Hz, 2H), 7.33 (d, J = 8.5 Hz, 1H), 7.45-7.48 (m, 3H), 65 118.9, 119.2, 119.5, 124.1, 128.5, 129.5, 130.5, 135.5, 148.0,
10 7.49-7.53 (m, 2H), 7.81-7.83 (m, 1H), 8.27-8.29 (m, 1H). 13C
NMR (125 MHz, CDCl3) δ 55.4, 115.0, 120.0, 120.9, 122.3,
124.2, 125.5, 126.3, 127.4, 127.7, 129.4, 130.5, 134.0, 147.7,
159.3. MS (ESI): 273 [M+Na]+; HRMS (ESI) calcd. for
158.1, 159.2. MS (ESI): 281 [M+H]+; HRMS (ESI) calcd. for
C18H17O3 [M+H]+: 281.1172; found: 281.1169. IR (KBr) ν 3451,
2921, 2848, 1627, 1603, 1577, 1511, 1428, 1375, 1282, 1242,
1162, 1099, 1017, 940, 876, 853, 829, 765, 715 cm-1.
o
1
C17H14NaO2 [M+Na]+: 273.0891; found: 273.0867. IR (KBr) ν 70 Compound 5j: brown solid (77.7 mg, 58%); mp: 95-97 C. H
15 3431, 1607, 1567, 1511, 1461, 1434, 1381, 1341, 1292, 1242,
1176, 1093, 1050, 1027, 879, 861, 834, 808, 781, 747, 713 cm-1.
Compound 5e: yellow solid (67.9 mg, 57%); mp: 110-112 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 5.67 (s, 1H), 7.19 (t, J = 8.5 Hz,
NMR (500 MHz, CDCl3, TMS) δ 3.92 (s, 3H), 5.62 (s, 1H), 7.11
(d, J = 2.5 Hz, 1H), 7.15-7.21 (m, 3H), 7.26 (d, J = 8.5 Hz, 1H),
7.35 (d, J = 8.0 Hz, 1H), 7.47 (dd, J = 9.0, 5.5 Hz, 2H), 8.17 (d, J
= 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 55.3, 105.7, 116.4
2H), 7.29 (d, J = 8.5 Hz, 1H), 7.46-7.51(m, 5H), 7.80-7.82 (m, 75 (d, JC-F = 21.25 Hz), 118.1, 118.6, 119.2, 119.5, 124.1, 128.2,
20 1H), 8.26-8.28 (m, 1H). 13C NMR (125 MHz, CDCl3) δ 116.5 (d,
JC-F = 21.375 Hz), 120.29, 120.32, 122.3, 124.3, 125.6, 126.5,
127.5, 131.1 (d, JC-F = 8.00 Hz), 133.2 (d, JC-F = 3.25 Hz), 134.2,
147.7, 162.4 (d, JC-F = 246.375 Hz). MS (ESI): 239 [M+H]+;
131.1 (d, JC-F = 7.875 Hz), 133.4 (d, JC-F = 3.25 Hz), 135.7, 148.0,
158.3, 162.3 (d, JC-F = 246.00 Hz). MS (ESI): 291 [M+Na]+;
HRMS (ESI) calcd. for C17H13FNaO2 [M+Na]+: 291.0797; found:
291.0778. IR (KBr) ν 3497, 1630, 1597, 1573, 1507, 1424, 1375,
HRMS (ESI) calcd. for C16H12FO [M+H]+: 239.0867; found: 80 1288, 1262, 1219, 1023, 940, 877, 838, 765 cm-1.
25 239.0864. IR (KBr) ν 3259, 1600, 1564, 1511, 1365, 1328, 1219,
Compound 5k: yellow solid (67.4 mg, 51%); mp: 100-101 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 2.41 (s, 3H), 3.93 (s, 3H), 5.81
(s, 1H), 7.15 (dd, J = 9.0, 2.5 Hz, 1H), 7.19 (d, J = 8.5 Hz, 1H),
7.31 (d, J = 8.0 Hz, 2H), 7.38-7.41 (m, 3H), 7.55 (d, J = 2.5 Hz,
1156, 1090, 1043, 881, 838, 816, 748 cm-1.
Compound 5f: yellow solid (91.0 mg, 69%); mp: 79-81 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.42 (s, 3H), 3.91 (s, 3H), 5.86
(s, 1H), 7.10 (d, J = 2.5 Hz, 1H), 7.15 (dd, J = 9.0, 2.5 Hz, 1H), 85 1H), 7.70 (d, J = 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
o
1
30 7.21 (d, J = 7.5 Hz, 1H), 7.34-7.29 (m, 4H), 7.40 (t, J = 7.5 Hz,
1H), 8.19 (d, J = 9.0 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
21.5, 55.3, 105.7, 117.9, 119.0, 119.5, 119.6, 124.2, 126.3, 128.3,
128.4, 129.5, 130.0, 135.6, 137.4, 139.4, 148.0, 158.2. MS (ESI):
21.2, 55.3, 100.5, 119.1, 119.9, 121.8, 125.1, 125.2, 129.0, 129.1,
129.6, 130.2, 134.5, 137.6, 146.8, 157.6. MS (ESI): 287 [M+Na]+;
HRMS (ESI) calcd. for C18H16NaO2 [M+H]+: 287.1048; found:
287.1034. IR (KBr) ν 3543, 1627, 1603, 1573, 1504, 1461, 1424,
265 [M+H]+; HRMS (ESI) calcd. for C18H17O2 [M+H]+: 90 1371, 1269, 1215, 1146, 1023, 934, 879, 848, 823, 735, 722 cm-1.
o
35 265.1229; found: 265.1217. IR (KBr) ν 3557, 3438, 1627, 1603,
1577, 1511, 1428, 1371, 1292, 1265, 1215, 1199, 1162, 1010,
942, 872, 856, 823, 798, 761, 713 cm-1.
Compound 5l: brown solid (92.4 mg, 66%); mp: 79-81 C. 1H
NMR (500 MHz, CDCl3, TMS) δ 3.86 (s, 3H), 3.94 (s, 3H), 5.75
(s, 1H), 7.05 (d, J = 8.5 Hz, 2H), 7.15 (dd, J = 9.0, 2.5, Hz, 1H),
7.18 (d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.5 Hz, 1H), 7.44 (d, J = 8.5
Compound 5g: brown solid (71.3 mg, 54%); mp: 103-104 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 2.43 (s, 3H), 3.93 (s, 3H), 5.81 95 Hz, 2H), 7.55 (d, J = 2.5 Hz, 1H), 7.70 (d, J = 9.0 Hz, 1H). 13C
40 (s, 1H), 7.11 (d, J = 2.5 Hz, 1H), 7.15 (dd, J = 9.0, 2.5 Hz, 1H),
7.29-7.36 (m, 4H), 7.41 (d, J = 8.0 Hz, 2H), 8.18 (d, J = 9.0 Hz,
1H). 13C NMR (125 MHz, CDCl3) δ 21.2, 55.3, 105.7, 117.9,
119.0, 119.47, 119.51, 124.1, 128.4, 129.2, 130.3, 134.4, 135.6,
NMR (125 MHz, CDCl3) δ 55.4, 100.5, 115.0, 119.1, 119.9,
121.6, 125.1, 125.4, 129.1, 129.5, 129.6, 130.5, 146.8, 157.7,
159.3. MS (ESI): 303 [M+Na]+; HRMS (ESI) calcd. for
C18H16NaO3 [M+Na]+: 303.0997; found: 303.0975. IR (KBr) ν
137.4, 148.0, 158.2. MS (ESI): 265 [M+H]+; HRMS (ESI) calcd. 100 3444, 1630, 1603, 1577, 1517, 1461, 1424, 1375, 1282, 1109,
45 for C18H17O2 [M+H]+: 265.1229; found: 265.1216. IR (KBr) ν
3557, 3424, 1627, 1600, 1577, 1514, 1428, 1371, 1295, 1265,
1219, 1196, 1162, 1020, 944, 876, 856, 823, 796 cm-1.
1046, 1027, 932, 884, 851, 826, 738, 722 cm-1.
o
1
Compound 5m: yellow solid (66.8 mg, 53%); mp: 86-88 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.43 (s, 3H), 5.82 (s, 1H), 7.25
(td, J = 8.0, 2.5 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 7.5
Compound 5h: yellow solid (81.2 mg, 58%); mp: 121-123 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 3.83 (s, 3H), 3.91 (s, 3H), 5.94 105 Hz, 2H), 7.40 (d, J = 7.5 Hz, 2H), 7.45 (d, J = 8.0 Hz, 1H), 7.78
50 (s, 1H), 6.93 (dd, J = 8.5, 2.5 Hz, 1H), 7.03 (s, 1H), 7.08-7.10 (m,
2H), 7.15 (dd, J = 9.0, 2.5 Hz, 1H), 7.31 (d, J = 8.5 Hz, 1H), 7.35
(d, J = 8.5 Hz, 1H), 7.41 (t, J = 8.0 Hz, 1H), 8.19 (d, J = 9.0 Hz,
1H). 13C NMR (125 MHz, CDCl3) δ 55.2, 55.3, 105.7, 113.4,
(dd, J = 9.0, 5.5 Hz, 1H), 7.88 (dd, J = 10.5, 2.5 Hz, 1H). 13C
NMR (125 MHz, CDCl3) δ 21.2, 106.3 (d, JC-F = 22.25 Hz),
116.6 (d, JC-F = 25.25 Hz), 120.0, 122.0, 125.1 (d, JC-F = 9.00 Hz),
126.9 (d, JC-F = 2.5 Hz), 129.1, 129.8 (d, JC-F = 8.75 Hz), 130.4,
114.7, 118.0, 119.0, 119.3, 119.5, 121.3, 124.2, 128.1, 130.6, 110 131.1, 134.0, 138.0, 147.3 (d, JC-F = 5.375 Hz), 160.7 (d, JC-F
=
55 135.7, 138.9, 148.0, 158.3, 160.5. MS (ESI): 281 [M+H]+;
HRMS (ESI) calcd. for C18H17O3 [M+H]+: 281.1172; found:
243.375 Hz). MS (ESI): 275 [M+Na]+; HRMS (ESI) calcd. for
C17H13FNaO [M+Na]+: 275.0848; found: 275.0834. IR (KBr) ν
8
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Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

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Organic & Biomolecular Chemistry
3523, 1636, 1603, 1511, 1448, 1368, 1209, 1149, 1040, 944, 879,
823, 788, 738, 718 cm-1.
Compound 5n: brown solid (77.7 mg, 58%); mp: 99-101 C. H
305.1141. IR (KBr) ν 3470, 3060, 2928, 1670, 1600, 1494, 1444,
View Article Online
1348, 1252, 1076, 1023, 995, 944, 915, 8D89O,I:81601.1,083393/C, 57O9B10,1726013,A
753, 727 cm-1.
o
1
o
1
NMR (500 MHz, CDCl3, TMS) δ 3.84 (s, 3H), 5.80 (s, 1H), 7.03 60 Compound 6d: yellow solid (108.6 mg, 77%); mp: 76-78 C. H
5
(d, J = 9.0 Hz, 2H), 7.23 (dd, J = 8.5, 2.5 Hz, 1H), 7.25 (d, J =
9.0 Hz, 1H), 7.40-7.43 (m, 3H), 7.76 (dd, J = 9.0, 5.5 Hz, 1H),
7.87 (dd, J = 10.5, 2.5 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ
55.3, 106.2 (d, JC-F = 22.25 Hz), 115.1, 116.5 (d, JC-F = 25.375
NMR (500 MHz, CDCl3, TMS) δ 2.21-2.27 (m, 1H), 2.50-2.57
(m, 1H), 2.58 (s, 3H), 2.81-2.89 (m, 2H), 3.86 (s, 3H), 4.14 (s,
1H), 6.79 (d, J = 8.0 Hz, 1H), 6.90 (t, J = 8.0 Hz,1H), 7.09 (d, J =
1.5 Hz, 2H), 7.12 (td, J = 8.0, 1.5 Hz, 1H), 7.17 (d, J = 8.0 Hz,
65 1H), 7.64 (s, 1H). 13C NMR (125 MHz, CDCl3) δ 21.3, 25.8, 35.6,
55.4, 79.2, 109.5, 122.4, 125.1, 126.8, 127.7, 130.0, 132.6, 132.7,
137.0, 137.5, 139.0, 158.6, 201.2. MS (ESI): 305 [M+Na]+;
HRMS (ESI) calcd. for C18H18NaO3 [M+Na]+: 305.1154; found:
305.1121. IR (KBr) ν 3451, 3014, 2928, 2835, 1918, 1676, 1603,
70 1497, 1464, 1428, 1331, 1278, 1235, 1179, 1086, 1023, 964, 939,
899, 876, 829, 814, 793, 761, 746, 725 cm-1.
Hz), 119.9, 121.8, 125.1 (d, JC-F = 8.875 Hz), 127.0 (d, JC-F
=
10 1.875 Hz), 129.1, 129.8 (d, JC-F = 8.75 Hz), 130.4, 131.0, 147.3 (d,
JC-F = 5.25 Hz), 159.5, 160.2 (d, JC-F = 243.375 Hz). MS (ESI):
291 [M+Na]+; HRMS (ESI) calcd. for C17H13FNaO2 [M+Na]+:
291.0797; found: 291.0781. IR (KBr) ν 3444, 1610, 1507, 1448,
1371, 1282, 1235, 1152, 1040, 944, 874, 824, 722 cm-1.
15 Compound 5o: white solid (75.2 mg, 68%); mp: 205-207 C. H
NMR (500 MHz, DMSO-d6, TMS) δ 7.46 (d, J = 8.5 Hz, 1H),
7.49 (ddd, J = 8.0, 5.0, 1.0 Hz, 1H), 7.53-7.56 (m, 3H), 7.90 (dd,
J = 7.5, 2.5 Hz, 1H), 8.02 (dt, J = 8.0, 2.0 Hz, 1H), 8.30-8.32 (m,
o
1
o
1
Compound 6e: brown solid (124.3 mg, 92%); mp: 81-83 C. H
NMR (500 MHz, CDCl3, TMS) δ 2.23-2.29 (m, 1H), 2.54-2.61
(m, 4H), 2.86-2.94 (m, 2H), 4.02 (s, 1H), 6.79 (d, J = 8.0 Hz, 1H),
1H), 8.54 (dd, J = 5.0, 2.0 Hz, 1H), 8.82 (d, J = 2.0 Hz, 1H), 9.53 75 6.93 (t, J = 7.5 Hz, 1H), 7.13-7.24 (m, 4H), 7.82 (dd, J = 9.0, 3.0
20 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 120.0, 120.2, 122.4,
123.3, 125.4, 125.7, 126.4, 127.6, 128.0, 134.0, 134.6, 136.8,
147.4, 149.5, 150.1. MS (ESI): 222 [M+H]+; HRMS (ESI) calcd.
for C15H12NO [M+H]+: 222.0919; found: 222.0908. IR (KBr) ν
Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 21.3, 25.9, 35.4, 79.1,
113.4 (d, JC-F = 21.875 Hz), 121.4 (d, JC-F = 22.125 Hz), 125.2,
126.6, 127.9, 130.7 (d, JC-F = 7.125 Hz), 132.8, 133.4 (d, JC-F
6.25 Hz), 137.3, 138.7, 140.1 (d, JC-F = 3.00 Hz), 161.6 (d, JC-F
=
=
3054, 1567, 1504, 1481, 1385, 1312, 1189, 1106, 1040, 973, 952, 80 245.5 Hz), 200.2. MS (ESI): 293 [M+Na]+; HRMS (ESI) calcd.
25 889, 864, 818, 800, 746, 710 cm-1.
for C17H15FNaO2 [M+H]+: 293.0954; found: 293.0943. IR (KBr)
ν 3431, 1680, 1610, 1590, 1494, 1421, 1371, 1345, 1318, 1272,
1239, 1159, 1083, 962, 945, 889, 829, 809, 785, 756, 730 cm-1.
1
Compound 6a: red liquid (76.2 mg, 64%). H NMR (500 MHz,
CDCl3, TMS) δ 2.44 (td, J = 12.5, 5.0 Hz, 1H), 2.66-2.74 (m, 2H),
2.87-2.92 (m, 1H), 4.24 (s, 1H), 7.18 (d, J = 7.5 Hz, 1H), 7.24-
7.29 (m, 5H), 7.37 (t, J = 7.5 Hz, 1H), 7.50 (td, J = 7.5, 1.5 Hz,
30 1H), 8.17 (dd, J = 8.0, 1.0 Hz, 1H). 13C NMR (125 MHz, CDCl3)
δ 26.5, 36.5, 77.7, 126.0, 126.9, 127.6, 128.0, 128.4, 129.0, 131.7,
134.1, 141.0, 144.3, 200.6. MS (ESI): 261 [M+Na]+; HRMS (ESI)
calcd. for C16H14NaO2 [M+Na]+: 261.0891; found: 261.0874. IR
(neat) ν 3477, 3054, 3021, 2928, 1686, 1600, 1491, 1451, 1361,
35 1288, 1225, 1159, 1076, 990, 939, 887, 848, 761, 738 cm-1.
Compound 6b: white solid (109.7 mg, 87%); mp: 107-109 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 2.24-2.31 (m, 1H), 2.58 (s, 3H),
2.60-2.66 (m, 1H), 2.88-2.95 (m, 2H), 4.12 (s, 1H), 6.80 (d, J =
7.5 Hz, 1H), 6.91 (t, J = 7.5 Hz, 1H), 7.13 (td, J = 7.5, 1.0 Hz,
40 1H), 7.19 (d, J = 8.5 Hz, 2H), 7.39 (t, J = 7.5 Hz, 1H), 7.51 (td, J
= 7.5, 1.5 Hz, 1H), 8.18 (dd, J = 8.5, 1.0 Hz, 1H). 13C NMR (125
MHz, CDCl3) δ 21.3, 26.6, 35.4, 79.3, 125.2, 126.8, 127.0, 127.7,
127.8, 128.9, 132.0, 132.8, 134.0, 137.5, 138.9, 144.4, 201.3. MS
(ESI): 275 [M+Na]+; HRMS (ESI) calcd. for C17H16NaO2
45 [M+Na]+: 275.1048; found: 275.1038. IR (KBr) ν 3431, 2365,
1680, 1597, 1487, 1461, 1371, 1308, 1275, 1222, 1156, 1066,
977, 947, 886, 848, 806, 768, 756, 705 cm-1.
Acknowledgement
85 We thank Dr. Yin Wei for her kind discussion in preparation
the manuscript.
Notes and references
College of Chemistry and Materials Engineering, Wenzhou University,
Chashan University Town, Wenzhou, Zhejiang Province 325035,
90 People’s Republic of China. Fax: 86 57786689300; Tel: 86 57786689300;
E-mail: Shaolix@wzu.edu.cn
† Electronic Supplementary Information (ESI) available: [Copy of 1H and
13C NMR spectra of compounds 4-6]. See DOI: 10.1039/b000000x/
‡ Footnotes should appear here. These might include comments relevant
95 to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
1
For some reviews of α-arylation reactions, please see: (a) D. A.
Culkin and J. F. Hartwig, Acc. Chem. Res., 2003, 36, 234; (b) F.
Bellina and R. Rossi, Chem. Rev., 2010, 110, 1082; (c) C. C. C.
Johansson and T. J. Colacot, Angew. Chem. Int. Ed., 2010, 49, 676; (d)
P. Novak and R. Martin, Curr. Org. Chem., 2011, 15, 3233; (e) S. T.
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Spork and T. J. Donohoe, Org. Biomol. Chem., 2015, 13, 4367.
100
Compound 6c: white solid (115.7 mg, 82%); mp: 147-149 oC. 1H
NMR (500 MHz, CDCl3, TMS) δ 2.23-2.29 (m, 1H), 2.55-2.61
50 (m, 4H), 2.83-2.88 (m, 2H), 3.85 (s, 3H), 4.16 (s, 1H), 6.64 (d, J
= 2.5 Hz, 1H), 6.80 (d, J = 7.5 Hz,1H), 6.90-6.93 (m, 2H), 7.13
(td, J = 7.5, 1.0 Hz, 1H), 7.19 (d, J = 7.5 Hz, 1H), 8.15 (d, J = 9.0
Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 21.3, 27.0, 35.4, 55.5,
79.1, 112.6, 113.9, 125.1, 125.4, 126.9, 127.7, 130.3, 132.8,
55 137.6, 139.2, 147.1, 164.2, 199.7. MS (ESI): 305 [M+Na]+;
HRMS (ESI) calcd. for C18H18NaO3 [M+Na]+: 305.1154; found:
105 2 (a) S. Lee, N. A. Beare and J. F. Hartwig, J. Am. Chem. Soc., 2001,
123, 8410; (b) M. S. Viciu, R. F. Germaneau and S. P. Nolan, Org.
Lett., 2002, 4, 4053; (c) M. S. Viciu, R. A. Kelly, III, E. D. Stevens,
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Navarro, N. Marion, N. M. Scott, J. González, D. Amoroso, A. Bell
110
and S. P. Nolan, Tetrahedron, 2005, 61, 9716;. (e) O. Navarro, N.
Marion, Y. Oonishi, R. A. Kelly, III and S. P. Nolan, J. Org. Chem.,
2006, 71, 685; (f) N. Marion, E. C. Ecarnot, O. Navarro, D.
Amoroso, A. Bell and S. P. Nolan, J. Org. Chem., 2006, 71, 3816;
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Journal Name, [year], [vol], 00–00 | 9

Organic & Biomolecular Chemistry
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Zhang, X.-Q. Yang, X.-L. Cui and Y.-J. Wu, Tetrahedron, 2011, 67,
8800.
5 3 For the synthesis of NHC-Pd(II)-Im complex 1, please see: (a) L.
Zhu, T.-T. Gao and L.-X. Shao, Tetrahedron, 2011, 67, 5150; (b) H.
Lv, L. Zhu, Y.-Q. Tang and J.-M. Lu, Appl. Organometal. Chem.,
2014, 28, 27.
4
For some selected examples, please see: (a) X.-X. Zhou and L.-X.
Shao, Synthesis, 2011, 3138; (b) Z.-S. Gu, L.-X. Shao and J.-M. Lu,
J. Organomet. Chem., 2012, 700, 132;. (c) W.-X. Chen and L.-X.
Shao, J. Org. Chem., 2012, 77, 9236; (d) T.-T. Gao, A.-P. Jin and
L.-X. Shao, Beilstein J. Org. Chem., 2012, 8, 1916; (e) L. Zhu, Y.-
M. Ye and L.-X. Shao, Tetrahedron, 2012, 68, 2414; (f) X.-B. Shen,
Y. Zhang, W.-X. Chen, Z.-K. Xiao, T.-T. Hu and L.-X. Shao, Org.
Lett., 2014, 16, 1984; (g) Z.-S. Gu, W.-X. Chen and L.-X. Shao, J.
Org. Chem., 2014, 79, 5806; (h) Y.-Y. Ji, L.-L. Lu, Y.-C. Shi and
L.-X. Shao, Org. Biomol. Chem., 2014, 12, 8488. (i) Z.-K. Xiao and
L.-X. Shao, Synthesis, 2012, 44, 711; (j) Z.-K. Xiao, H.-Y. Yin and
L.-X. Shao, Org. Lett., 2013, 15, 1254; (k) H.-Y. Yin, M.-Y. Liu
and L.-X. Shao, Org. Lett., 2013, 15, 6042; (l) Z.-K. Xiao, H.-Y.
Yin and J.-M. Lu, Inorg. Chim. Acta, 2014, 423, 106.
10
15
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35
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50
5
(a) D. J. Collins, J. D. Cullen, G. D. Fallon and B. M. Gatehouse,
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Collins, J. A. Cullen and G. M. Stone, Aust. J. Chem., 1988, 41, 745;
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Med. Chem., 1988, 31, 107; (e) H. Ishii, T. Ishikawa, S. Takeda, M.
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Ishikawa, M. Murota, T. Watanabe, T. Harayama and H. Ishii,
Tetrahedron Lett., 1995, 36, 4269; (g) A. Kamada, A. Sasaki, N.
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