Copper-catalyzed trifluoromethylation-cyclization of enynes: Highly regioselective construction of trifluoromethylated carbocycles and heterocycles

Article abstract of DOI:10.1002/chem.201303025

Regioselective trifluoromethylation-cyclization: A method for copper-catalyzed trifluoromethylation-cyclization of simple enynes using the C-C triple bond as a nucleophile is reported for the first time (see scheme). The reaction proceeds efficiently in a

Full text of DOI:10.1002/chem.201303025

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013
Copper-Catalyzed Trifluoromethylation–Cyclization of Enynes: Highly
Regioselective Construction of Trifluoromethylated Carbocycles and
Heterocycles
Pin Gao, Xiao-Biao Yan, Tao Tao, Fan Yang, Ting He, Xian-Rong Song,
[
a]
Xue-Yuan Liu,* and Yong-Min Liang*
chem_201303025_sm_miscellaneous_information.pdf

Supporting Information
Table of Contents
1
2
3
4
5
6
7
8
9
General remarks
S2
General procedure for the synthesis of enynes
Characterization data of enynes
S2-S4
S5- S14
S15
General experimental procedure of 3a-3u, 3y
Characterization data of 3a-3u, 3y, 5
References
S15-S27
S27
Mechanistic experiment: Reaction of 1a in the presence of TEMPO:
Crystallographic data of 3a and 3s
S28
S29-S30
S31-S76
1
13
H NMR and C NMR spectra of 3a-3u, 3y, 5
S1

1
. General remarks
Column chromatography was carried out on silica gel and analytical TLC was performed
1
with silica gel GF254 plates. NMR spectra were recorded in CDCl
3
at 400 MHz ( H NMR),
13
19
1
00 MHz ( C NMR) and 376 MHz ( F NMR). IR spectra were recorded on a FT-IR
-
1
spectrometer and only major peaks are reported in cm . Data collections for crystal structure
were performed at room temperature (293 K). All trifluoromethylation products were further
1
13
C
characterized by high resolution mass spectra (HRMS); copies of their H NMR and
NMR spectra are provided.
Unless otherwise noted, materials obtained from commercial suppliers were used without
further purification. CH Cl was dried and distilled from CaH . Togni’s reagent was prepared
according to literature procedures. All reactions were carried out under Ar atmosphere.
2
2
2
2
. General procedure for the synthesis of enynes:
. Enynes 1a-1k, 1m were prepared in the same method:
-Methyl-N-(2-methyl-allyl)-N-prop-2-ynyl-benzene-sulfonamide (S2)
1
[1]
4
[
2]
To a solution of S1 (5.23 g, 25.0 mmol) and acetone (150 mL) at 0 °C K
2 3
CO (5.25 g,
38.0 mmol) and 3-bromo-2-methyl-propene (5.40 g, 40.0 mmol) were added. The resulting
mixture was heated under reflux for 5 h. Stirring was continued at room temperature for 16 h.
The solvent was removed under reduced pressure and the resulting solid was dissolved in
ethyl acetate, washed with water and brine and dried over MgSO
4
. The solvent was removed
under reduced pressure and the crude product was purified by SiO
2
chromatography to give
S2.
To a dried schlenk flask was added Pd(PPh
3
)
2
Cl
2
(0.2 mmol), CuI (0.2 mmol), iodoarene
N under argon. The resulting
(
11.0 mmol), S2 (2.63 g, 10.0 mmol) and freshly distilled Et
3
mixture was stirred for 16 h at 50 °C. 50 mL of MTBE were added and the mixture filtered.
S2

After removal of solvent using rotary evaporator, the crude compound was purified by SiO
2
chromatography to give 1a-1k.
[
3]
2
. Enynes 1l was prepared in the method :
To a cold solution (0 °C) of the starting alcohol in MeCN were successively added MsCl
and Et N and the mixture was allowed to warm to rt. After 1 h, K CO and TsNH were added
3
2
3
2
and the mixture which was heated to 80 °C overnight. Once back to rt, the mixture was
directly purified by flash chromatography eluting first with petroleum ether and then with
petroleum ether/ethyl acetate (9:1) to give S3
2 3
To a solution of S3 (25.0 mmol) and acetone (150 mL) at 0 °C K CO (5.25 g, 38.0 mmol)
and 3-bromo-2-methyl-propene (5.40 g, 40.0 mmol) were added. The resulting mixture was
heated under reflux for 5 h. Stirring was continued at room temperature for 16 h. The solvent
was removed under reduced pressure and the resulting solid was dissolved in ethyl acetate,
washed with water and brine and dried over MgSO
4
. The solvent was removed under reduced
pressure and the crude product was purified by SiO
2
chromatography to give S4 as a white
solid.
To a dried schlenk flask was added Pd(PPh
11.0 mmol), S4 (10.0 mmol) and freshly distilled Et
was stirred for 16 h at 50 °C. 50 mL of MTBE were added and the mixture filtered. After
) Cl
3 2 2
(0.2 mmol), CuI (0.2 mmol), iodobenzene
(
3
N under argon. The resulting mixture
removal of solvent using rotary evaporator, the crude product was purified by SiO
2
chromatography to give 1l.
[
4]
3
. Enynes 1n - 1p were prepared in the same method :
S3

.
To a solution of arylpropargyl alcohol (4.0 mmol) in freshly distilled THF (8 mL) was
added NaH (0.144 g, 6 mmol, freshly pre-washed with dry hexane) portionwise under
nitrogen atmosphere at 0 ºC. The white suspension was slowly warmed to room temperature
and stirred for 2 hours. The reaction mixture was then cooled to 0 °C and
3-bromo-2-methyl-1-propene (1.08 g, 8 mmol) was added dropwise. After complete addition,
the reaction was warmed to room temperature and further stirred for 2 hours. Water (~10 mL)
was slowly added and the aqueous layer was extracted with diethyl ether (3 × 20 mL). The
combined organic layers were washed with water, brine and dried over sodium sulfate.
Solvent was removed by rotary evaporation and the crude product was purified by SiO
2
chromatography to give 1n-1p as a colorless liquid.
[
7]
4
. Enynes 1s – 1u were prepared in the same method :
To a solution of 4-methyl-N-(prop-2-ynyl)benzenesulfonamide (209.3 mg, 1.0 mmol) in
CH Cl (5 mL) was added iPr NEt (194.0 mg, 1.5 mmol) and then cooled to 0 ºC in the ice
2
2
2
water bath. Methacryloyl chloride (108.6 mg, 1.2 mmol) was slowly added to the solution at 0
ºC and then the mixture was stirred at room temperature for 1 h. The reaction was quenched
by water and the aqueous layer was extracted with CH
2 2
Cl (10 mL x 3). The combined
organic layers were washed with brine, dried over Na SO
2
4
and concentrated in vacuo. The
residue was purified by flash column chromatography (n-hexane/AcOEt = 3:1) to afford S5
as a white solid.
To a dried schlenk flask was added Pd(PPh
3
)
2
Cl
2
(0.2 mmol), CuI (0.2 mmol), Iodobenzene
N under argon. The resulting mixture
(
11.0 mmol), S5 (10.0 mmol) and freshly distilled Et
3
was stirred for 16 h at 50 °C. 50 mL of MTBE were added and the mixture filtered. After
removal of solvent using rotary evaporator, the residue was purified by flash column
chromatography to afford 1s-1u.
S4

3
. Characterization data of enynes:
1
H
4-methyl-N-(2-methylallyl)-N-(3-phenylprop-2-yn-1-yl)benzenesulfonamide (1a) :
3
NMR (400 MHz, CDCl ) δ 1.81 (s, 3H), 2.32 (s, 3H), 3.80 (s, 2H), 4.26 (s, 2H), 5.01 (s, 2H),
1
3
7
.02-7.04 (m, 2H), 7.20-7.29 (m, 5H), 7.78 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
)
δ 143.4, 139.3, 136.0, 131.4, 129.5, 128.3, 128.1, 127.8, 122.2, 115.5, 85.7, 81.6, 52.7, 36.4,
21.4, 19.7.
1
H
4-methyl-N-(2-methylallyl)-N-(3-(p-tolyl)prop-2-yn-1-yl)benzenesulfonamide (1b) :
3
NMR (400 MHz, CDCl ) δ 1.81 (s, 3H), 2.32 (s, 3H), 2.34 (s, 3H), 3.80 (s, 2H), 4.25 (s, 2H),
5.00 (m, 2H), 6.93 (d, J = 8.0 Hz, 2H), 7.03 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.8 Hz, 2H), 7.77
1
3
(
d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 143.3, 139.4, 138.5, 136.2, 131.4, 129.5,
128.8, 127.8, 119.2, 115.5, 85.8, 80.9, 52.7, 36.5, 21.4, 19.8.
TsN
1
4
-methyl-N-(2-methylallyl)-N-(3-(m-tolyl)prop-2-yn-1-yl)benzenesulfonamide (1c) : H
3
NMR (400 MHz, CDCl ) δ 1.81 (s, 3H), 2.29 (s, 3H), 2.34 (s, 3H), 3.80 (s, 2H), 4.25 (s, 2H),
S5

1
3
5
.00 (s, 2H), 6.85 (s, 2H), 7.07-7.14 (m, 2H), 7.25-7.27 (m, 2H), 7.78 (d, J = 8.4 Hz, 2H); C
NMR (100 MHz, CDCl ) δ 143.3, 139.3, 137.7, 136.1, 132.0, 129.5, 129.2, 128.6, 128.0,
27.8, 122.1, 115.5, 85.8, 81.2, 52.7, 36.4, 21.4, 21.2, 19.7.
3
1
N-(3-(4-methoxyphenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1d) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.34 (s, 3H), 3.79 (s, 5H), 4.24 (s, 2H),
5
2
1
.00 (d, J = 5.2 Hz, 2H), 6.75 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 2H), 7.25 (d, J = 8.8 Hz,
1
3
H), 7.77 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 159.6, 143.3, 139.4, 136.2,
32.9, 129.4, 127.8, 115.4, 114.4, 113.7, 85.5, 80.2, 55.3, 52.6, 36.5, 21.4, 19.7.
N-(3-(2-methoxyphenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1e) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.27 (s, 3H), 3.79 (s, 3H), 3.82 (s, 2H), 4.31
(s, 2H), 5.00 (s, 1H), 5.07 (s, 1H), 6.79-6.82 (m, 2H), 6.87-6.89 (m, 1H), 7.19 (d, J = 8.0 Hz,
1
3
2
1
3
3
H), 7.22-7.26 (m, 1H), 7.77 (d, J = 8.0 Hz, 2H); C NMR (100 MHz, CDCl ) δ 159.9, 143.2,
39.2, 136.0, 133.3, 129.7, 129.3, 127.8, 120.0, 115.5, 111.5, 110.4, 85.6, 82.3, 55.5, 52.4,
6.7, 21.3, 19.7.
S6

TsN
F
N-(3-(2-fluorophenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1f) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.26 (s, 3H), 3.81 (s, 2H), 4.29 (s, 2H), 5.00
(s, 1H), 5.04 (s, 1H), 6.97-7.04 (m, 3H), 7.21 (d, J = 8.0 Hz, 2H), 7.23-7.29 (m, 1H), 7.76 (d,
1
3
J = 8.0 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 162.6 (d, J = 251.0 Hz), 143.4, 139.1, 135.8,
133.3 (d, J = 1.0 Hz), 130.1 (d, J = 8.0 Hz), 129.4, 127.7, 123.7 (d, J = 3.0 Hz), 115.7, 115.3
(d, J = 20.0 Hz), 110.8 (d, J = 16.0 Hz), 86.9 (d, J = 3.0 Hz), 79.2, 52.7, 36.4, 21.3, 19.7.
TsN
F
N-(3-(4-fluorophenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1g) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.33 (s, 3H), 3.79 (s, 2H), 4.24 (s, 2H), 5.00
(s, 2H), 6.92 (t, J = 8.8 Hz, 2H), 7.00-7.04 (m, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.4
1
3
Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 162.3 (d, J = 249.0 Hz), 143.3, 139.2, 136.0, 133.3
(
(
d, J = 9.0 Hz), 129.4, 127.8, 118.2 (d, J = 4.0 Hz), 115.5, 115.3 (d, J = 22.0 Hz), 84.5, 81.3
d, J = 1.0 Hz), 52.7, 36.3, 21.3 (d, J = 3.0 Hz), 19.7.
TsN
F
S7

N-(3-(3-fluorophenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1h) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.35 (s, 3H), 3.80 (s, 2H), 4.24 (s, 2H),
5.00 (s, 2H), 6.63 (d, J = 9.2 Hz, 1H), 6.84 (d, J = 8.0 Hz, 1H), 6.96-7.00 (m, 1H), 7.17-7.22
1
3
(
m, 1H), 7.27 (d, J = 8.0 Hz, 2H), 7.77 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ
1
3
8
62.1 (d, J = 245.0 Hz), 143.6, 139.2, 136.1, 129.7 (d, J = 9.0 Hz), 129.5, 127.8, 127.2 (d, J =
.0 Hz), 124.0 (d, J = 10.0 Hz), 118.3 (d, J = 22.0 Hz), 115.8, 115.6, 84.4 (d, J = 3.0 Hz),,
2.7, 52.8, 36.2, 21.3, 19.7.
N-(3-(4-chlorophenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1i) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.34 (s, 3H), 3.78 (s, 2H), 4.24 (s, 2H), 5.00
1
3
(
s, 2H), 6.96 (d, J = 8.4 Hz, 2H), 7.20-7.26 (m, 4H), 7.77 (d, J = 8.0 Hz, 2H); C NMR (100
) δ 143.4, 139.3, 136.1, 134.4, 132.7, 129.5, 128.4, 127.8, 120.7, 115.6, 84.5,
2.8, 52.8, 36.3, 21.4, 19.7.
MHz, CDCl
3
8
methyl
4-(3-(4-methyl-N-(2-methylallyl)phenylsulfonamido)prop-1-yn-1-yl)benzoate
) δ 1.81 (s, 3H), 2.33 (s, 3H), 3.80 (s, 2H), 3.91 (s, 3H), 4.27
1
(
1j) : H NMR (400 MHz, CDCl
3
(s, 2H), 5.00 (s, 2H), 7.08 (d, J = 8.4 Hz, 2H), 7.25 (d, J = 8.4 Hz, 2H), 7.77 (d, J = 8.0 Hz,
13
2
3
H), 7.90 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl ) δ 166.3, 143.5, 139.2, 136.0,
S8

131.3, 129.7, 129.5, 129.2, 127.8, 126.8, 115.6, 84.9, 84.8, 52.8, 52.2, 36.3, 21.4, 19.7.
N-(3-(2-cyanophenyl)prop-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide
1
(
1k) : H NMR (400 MHz, CDCl
3
) δ 1.81 (s, 3H), 2.19 (s, 3H), 3.90 (s, 2H), 4.32 (s, 2H),
5.03 (s, 1H), 5.12 (s, 1H), 7.17-7.20 (m, 3H), 7.36-7.40 (m, 1H), 7.47-7.51 (m, 1H), 7.57-7.59
1
3
(
m, 1H), 7.77 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 143.4, 139.0, 135.9, 132.4,
32.3, 132.1, 129.4, 128.5, 127.8, 126.2, 117.2, 116.1, 115.1, 88.6, 81.7, 52.9, 36.2, 21.2,
9.7.
1
1
1
4
-methyl-N-(2-methylallyl)-N-(4-phenylbut-3-yn-1-yl)benzenesulfonamide (1l) : H NMR
) δ 1.73 (s, 3H), 2.41 (s, 3H), 2.64 (t, J = 7.6 Hz, 2H), 3.35 (t, J = 7.6 Hz,
H), 3.78 (s, 2H), 4.94 (m, 2H), 7.26-7.30 (m, 5H), 7.33-7.36 (m, 2H), 7.73 (d, J = 8.0 Hz,
(400 MHz, CDCl
3
2
2
1
1
3
3
H); C NMR (100 MHz, CDCl ) δ 143.3, 140.5, 136.8, 131.5, 129.7, 128.2, 127.8, 127.1,
23.3, 114.9, 86.5, 82.1, 55.0, 46.6, 21.5, 19.8, 19.8.
4-methyl-N-(2-methylallyl)-N-(3-(thiophen-2-yl)prop-2-yn-1-yl)benzenesulfonamide
S9

1
(
1m) : H NMR (400 MHz, CDCl
3
) δ 1.80 (s, 3H), 2.37 (s, 3H), 3.77 (s, 2H), 4.26 (s, 2H),
5.00 (s, 2H), 6.90 (d, J = 3.2 Hz, 2H), 7.19 (t, J = 3.2 Hz, 1H), 7.28 (d, J = 8.0 Hz, 2H), 7.76
1
3
(
d, J = 8.0 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 143.5, 139.2, 135.8, 132.1, 129.5, 127.7,
127.1, 126.7, 122.1, 115.6, 85.6, 78.9, 52.7, 36.5, 21.5, 19.7.
1
(
3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene (1n) : H NMR (400 MHz, CDCl
3
) δ 1.78 (s,
3
7
8
H), 4.04 (s, 2H), 4.36 (s, 2H), 4.95 (s, 1H), 5.03 (d, J = 0.4 Hz, 1H), 7.25-7.32 (m, 3H),
1
3
.44-7.46 (m, 2H); C NMR (100 MHz, CDCl
3
) δ 141.5, 131.7, 128.4, 128.2, 122.7, 113.0,
6.1, 85.2, 73.7, 57.7, 19.6.
1
1
-methyl-4-(3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzene (1o) : H NMR (400 MHz,
3
CDCl ) δ 1.78 (s, 3H), 2.34 (s, 3H), 4.03 (s, 2H), 4.34 (s, 2H), 4.94 (s, 1H), 5.02 (s, 1H), 7.11
13
(
3
d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H); C NMR (100 MHz, CDCl ) δ 141.6, 138.5,
131.6, 129.0, 119.6, 112.9, 86.2, 84.4, 73.6, 57.8, 21.4, 19.6.
1
methyl 4-(3-((2-methylallyl)oxy)prop-1-yn-1-yl)benzoate (1p) : H NMR (400 MHz,
3
CDCl ) δ 1.78 (s, 3H), 3.91 (s, 3H), 4.04 (s, 2H), 4.37 (d, J = 0.4 Hz, 2H), 4.96 (s, 1H), 5.03
S10

1
3
(
s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.98 (d, J = 7.6 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ
166.4, 141.3, 131.6, 129.6, 129.4, 127.3, 113.1, 88.3, 85.3, 73.8, 57.6, 52.2, 19.5.
[
5]
1
(
4-((2-methylallyl)oxy)but-1-yn-1-yl)benzene (1q) : H NMR (400 MHz, CDCl
3
) δ 1.75 (s,
3
7
1
H), 2.69 (t, J = 7.2 Hz, 2H), 3.59 (t, J = 7.2 Hz, 2H), 3.93 (s, 2H), 4.90 (s, 1H), 4.99 (s, 1H),
1
3
.22-7.28 (m, 3H), 7.38-7.40 (m, 2H); C NMR (100 MHz, CDCl
3
) δ 142.0, 131.5, 128.1,
27.6, 123.6, 112.2, 86.8, 81.4, 74.8, 68.1, 20.7, 19.3.
[6]
1
diethyl 2-(2-methylallyl)-2-(3-phenylprop-2-yn-1-yl)malonate (1r) : H NMR (400 MHz,
CDCl ) δ 1.27 (t, J = 6.8 Hz, 6H), 1.71 (s, 3H), 2.91 (s, 2H), 3.05 (s, 2H), 4.15-4.29 (m, 4H),
3
.90 (s, 1H), 4.93 (s, 1H), 7.26-7.28 (m, 3H), 7.36-7.38 (m, 2H); C NMR (100 MHz, CDCl )
3
1
3
4
δ 170.3, 140.1, 131.6, 128.2, 127.9, 123.3, 116.2, 84.8, 83.7, 61.6, 56.7, 39.6, 23.5, 23.3, 14.0.
O
TsN
1
N-(3-phenylprop-2-yn-1-yl)-N-tosylmethacrylamide (1s) : H NMR (400 MHz, CDCl
3
) δ
1.95 (s, 3H), 2.40 (s, 3H), 4.88 (s, 2H), 5.29 (s, 1H), 5.36 (d, J = 1.2 Hz, 1H), 7.27-7.33 (m,
S11

1
3
7
1
3
H), 8.00 (d, J = 8.4 Hz, 2H); C NMR (100 MHz, CDCl ) δ 171.4, 144.9, 139.5, 136.0,
31.6, 129.3, 128.8, 128.7, 128.3, 122.0, 119.5, 84.7, 83.8, 37.7, 21.6, 19.6.
1
N-(3-(p-tolyl)prop-2-yn-1-yl)-N-tosylmethacrylamide (1t) : H NMR (400 MHz, CDCl
3
) δ
1
7
2
1
.94 (s, 3H), 2.35 (s, 3H), 2.41 (s, 3H), 4.88 (s, 2H), 5.29 (s, 1H), 5.36 (d, J = 1.2 Hz, 1H),
.11 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.4 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 8.00 (d, J = 8.4 Hz,
1
3
H); C NMR (100 MHz, CDCl
3
) δ 171.5, 144.8, 139.6, 138.9, 136.0, 131.5, 129.3, 129.1,
28.8, 119.5, 118.9, 84.9, 83.2, 37.9, 21.5, 19.6.
1
methyl 4-(3-(N-tosylmethacrylamido)prop-1-yn-1-yl)benzoate (1u) : H NMR (400 MHz,
CDCl ) δ 1.95 (s, 3H), 2.41 (s, 3H), 3.93 (s, 3H), 4.89 (s, 2H), 5.27 (s, 1H), 5.37 (d, J = 0.8
Hz, 1H), 7.29 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.98 (dd, J = 8.4 Hz, J = 1.2 Hz,
) δ 171.3, 166.3, 145.0, 139.6, 135.9, 131.5, 130.0, 129.4,
3
1
2
1
3
2
H); C NMR (100 MHz, CDCl
3
129.4, 128.7, 126.6, 119.7, 86.8, 83.8, 52.3, 37.5, 21.6, 19.5.
BnN
S12

[8]
1
N-benzyl-2-methyl-N-(3-phenylprop-2-yn-1-yl)prop-2-en-1-amine (1v) : H NMR (400
MHz, CDCl ) δ 1.81 (s, 3H), 3.14 (s, 2H), 3.49 (s, 2H), 3.68 (s, 2H), 4.91 (s, 1H), 5.02 (d, J =
.8 Hz, 1H), 7.23-7.27 (m, 1H), 7.31-7.34 (m, 5H), 7.39-7.41 (m, 2H), 7.46-7.48 (m, 2H); C
NMR (100 MHz, CDCl ) δ 143.1, 139.1, 131.7, 129.0, 128.3, 127.9, 127.0, 123.5, 113.4, 85.5,
4.6, 60.4, 57.2, 42.1, 20.7.
3
13
0
3
8
[1b]
1
N-(but-2-yn-1-yl)-4-methyl-N-(2-methylallyl)benzenesulfonamide (1w) : H NMR (400
MHz, CDCl ) δ 1.50 (t, J = 2.4 Hz, 3H), 1.76 (s, 3H), 2.43 (s, 3H), 3.70 (s, 2H), 3.97 (d, J =
.4 Hz, 2H), 4.95 (d, J = 0.8 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H); C
NMR (100 MHz, CDCl ) δ 143.1, 139.5, 136.2, 129.1, 127.9, 115.1, 81.5, 71.5, 52.4, 36.0,
3
13
2
3
21.5, 19.7, 3.16.
TsN
N
[9]
4-methyl-N-(2-methylallyl)-N-(3-(pyridin-2-yl)prop-2-yn-1-yl)benzenesulfonamide
1
(
1x) : H NMR (400 MHz, CDCl
3
) δ 1.76 (s, 3H), 2.45 (s, 3H), 3.66 (d, J = 12.8 Hz, 1H),
4.43 (d, J = 12.8 Hz, 1H), 4.62 (s, 1H), 4.67 (s, 1H), 6.07 (d, J = 4.0 Hz, 1H), 6.28 (d, J = 4.0
Hz, 1H), 6.56 (t, J = 6.4 Hz, 1H), 6.70-6.74 (m, 1H), 7.30 (d, J = 8.0 Hz, 3H), 7.56 (d, J = 8.0
1
3
Hz, 2H), 8.21 (d, J = 7.2 Hz, 1H); C NMR (100 MHz, CDCl
3
) δ 143.9, 139.4, 134.0, 131.4,
129.4, 128.3, 122.4, 119.0, 118.8, 118.0, 115.8, 110.5, 110.4, 97.6, 59.1, 21.6, 20.2.
S13

TsN
1
H
4-methyl-N-(2-phenylallyl)-N-(3-phenylprop-2-yn-1-yl)benzenesulfonamide (1y) :
3
NMR (400 MHz, CDCl ) δ 2.32 (s, 3H), 4.20 (s, 2H), 4.33 (s, 2H), 5.38 (s, 1H), 5.60 (s, 1H),
7.03 (d, J = 7.2 Hz, 2H), 7.21-7.37 (m, 8H), 7.57 (d, J = 6.8 Hz, 2H), 7.79 (d, J = 8.0 Hz, 2H);
1
3
3
C NMR (100 MHz, CDCl ) δ 143.5, 141.4, 137.7, 135.6, 131.4, 129.5, 128.4, 128.3, 128.2,
128.1, 127.9, 126.4, 122.2, 117.2, 86.1, 81.4, 50.3, 36.4, 21.4.
1
N-allyl-4-methyl-N-(3-phenylprop-2-yn-1-yl)benzenesulfonamide (1z) : H NMR (400
MHz, CDCl ) δ 2.32 (s, 3H), 3.89 (d, J = 6.4 Hz, 2H), 4.30 (s, 2H), 5.25-7.35 (m, 2H),
.75-5.85 (m, 1H), 7.06 (d, J = 6.8 Hz, 2H), 7.21-7.29 (m, 5H), 7.77 (d, J = 8.4 Hz, 2H); C
NMR (100 MHz, CDCl ) δ 143.4, 135.9, 132.0, 131.4, 129.5, 128.3, 128.0, 127.7, 122.1,
19.8, 85.6, 81.6, 49.2, 36.7, 21.3.
3
13
5
3
1
S14

4
. General experimental procedure
General producedure for carbotrifloromethylation/cyclization of enynes 1 : In a glass tube,
Togni’s reagent 2 ( 126.0 mg, 0.4 mmol) and Cu(CH CN) PF (15.2 mg, 0.04 mmol) were
3
4
6
successively added to a solution of 1 (0.2 mmol) in DCM (2.0 mL). The reactor was flushed
with argon and sealed. The reaction mixture was stirring at 50 °C for 20 hour and then
concentrated in vacuo. The residue was purified by column chromatography (silica gel,
appropriate mixture of n-hexane/ethyl acetate) to afford 3.
5
. Characterization data of 3a-3u
CF3
TsN
O
O
I
(Z)-(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(phenyl)methyl
1
2
-iodobenzoate (3a) : 83% yield, white solid. Mp = 150-152 ℃. H NMR (400 MHz, CDCl
3
)
δ 1.25 (s, 3H), 1.94-2.21 (m, 2H), 2.45 (s, 3H), 3.23 (q, J = 9.6 Hz, 2H), 3.92 (d, J = 14.8 Hz,
1H), 4.11 (d, J = 14.8 Hz, 1H), 7.16-7.20 (m, 1H), 7.35-7.45 (m, 8H), 7.72 (d, J = 8.4 Hz, 2H),
1
3
7
.76 (dd, J
1
= 7.6 Hz, J
) δ 163.4, 144.1, 141.9, 141.7, 133.6, 133.4, 133.2, 133.1, 131.6, 131.4, 130.1,
29.8, 129.8, 128.5, 128.0, 128.0, 125.8 (q, J = 277.0 Hz), 94.5, 59.5, 50.1, 41.5, 40.6 (q, J =
2 1 2
= 1.6 Hz, 1H), 8.01 (dd, J = 8.0 Hz, J = 0.8 Hz, 1H); C NMR (100
MHz, CDCl
3
1
2
1
19
-1
3
7.0 Hz), 24.3, 21.5; F NMR (376 MHz, CDCl ) δ – 60.3; IR (thin film, cm ) 2924, 2851,
741, 1641, 1489, 1461, 1351, 1261, 1236, 1164, 1135, 1044, 815, 743; HRMS (ESI) calcd
+
25
for C28H F
3
INO
4
S [M+H] : 656.0574, found: 656.0565.
(Z)-(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(p-tolyl)methyl
S15

1
2
-iodobenzoate (3b) : 77% yield, white solid. Mp = 166-168 ℃. H NMR (400 MHz, CDCl
δ 1.26 (s, 3H), 2.01-2.21 (m, 2H), 2.34 (s, 3H), 2.44 (s, 3H), 3.23 (q, J = 9.6 Hz, 2H), 3.91 (d,
J = 14.8 Hz, 1H), 4.10 (d, J = 14.4 Hz, 1H), 7.18 (d, J = 7.6 Hz, 3H), 7.31-7.41 (m, 5H), 7.71
3
)
1
3
(
d, J = 8.0 Hz, 2H), 7.75 (dd, J
MHz, CDCl ) δ 163.4, 144.0, 142.1, 141.6, 139.9, 133.4, 133.3, 131.7, 131.4, 130.2, 130.0,
29.9, 129.8, 129.1, 127.9, 125.9 (q, J = 277.0 Hz), 94.4, 59.5 (d, J = 1.9 Hz), 50.1, 41.5, 40.5
1 2
= 8.0 Hz, J = 1.6 Hz, 1H), 7.99-8.01 (m, 1H); C NMR (100
3
1
19
-1
(
3
q, J = 27.2 Hz), 24.3, 21.5, 21.3; F NMR (376 MHz, CDCl ) δ – 60.3; IR (thin film, cm )
2924, 2857, 1741, 1643, 1509, 1431, 1381, 1351, 1261, 1236, 1164, 1130, 1043, 820, 743;
+
HRMS (ESI) calcd for C29
H
27
F
3
INO
4
S [M+H] : 670.0730, found: 670.0726.
(Z)-(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(m-tolyl)methyl
1
2
3
-iodobenzoate (3c) : 76% yield, white solid. Mp = 124-126 ℃. H NMR (400 MHz, CDCl )
δ 1.26 (s, 3H), 1.94-2.21 (m, 2H), 2.34 (s, 3H), 2.45 (s, 3H), 3.22 (q, J = 10.0 Hz, 2H), 3.91 (d,
J = 14.8 Hz, 1H), 4.10 (d, J = 14.4 Hz, 1H), 7.16-7.29 (m, 5H), 7.34-7.42 (m, 3H), 7.71 (d, J
=
8.4 Hz, 2H), 7.76 (dd, J
1
= 8.0 Hz, J
C NMR (100 MHz, CDCl ) δ 163.4, 144.1, 142.1, 141.6, 138.2, 133.3, 133.3, 133.1, 131.7,
31.4, 130.6, 130.5, 129.8, 128.3, 128.0, 128.0, 127.1, 125.9 (q, J = 277.0 Hz), 94.5, 59.5,
2 1 2
= 1.6 Hz, 1H), 8.01 (dd, J = 8.0 Hz, J = 0.8 Hz, 1H);
1
3
3
1
5
19
3
0.1, 41.5 (d, J = 1.2 Hz), 40.5 (q, J = 27.0 Hz), 24.3, 21.5, 21.3; F NMR (376 MHz, CDCl )
-1
δ – 60.3; IR (thin film, cm ) 2923, 2856, 1741, 1599, 1582, 1461, 1351, 1262, 1240, 1164,
+
1132, 1044, 815, 789, 756; HRMS (ESI) calcd for C29
27
H F
3
INO
4
S [M+H] : 670.0730, found:
670.0724.
S16

(Z)-(4-methoxyphenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)met
1
hyl 2-iodobenzoate (3d) : 82% yield, white solid. Mp = 67-69 ℃. H NMR (400 MHz,
CDCl
3
) δ 1.26 (s, 3H), 1.98-2.24 (m, 2H), 2.44 (s, 3H), 3.22 (q, J = 9.6 Hz, 2H), 3.80 (s, 3H),
.90 (d, J = 14.4 Hz, 1H), 4.09 (d, J = 14.4 Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 7.15-7.19 (m,
H), 7.34-7.41 (m, 5H), 7.71 (d, J = 8.0 Hz, 2H), 7.75 (dd, J = 7.6 Hz, J = 1.6 Hz, 1H), 8.00
) δ 163.5, 160.4, 144.0, 141.9, 141.6, 133.5,
33.4, 133.3, 131.7, 131.5, 131.3, 129.8, 128.0, 128.0, 125.9 (q, J = 277.0 Hz), 125.3, 113.8,
3
1
1
2
1
3
(d, J= 8.0 Hz, 1H); C NMR (100 MHz, CDCl
3
1
1
9
9
4.4, 59.5 (d, J = 2.0 Hz), 55.2, 50.1, 41.5, 40.5 (q, J = 27.1 Hz), 24.3, 21.5; F NMR (376
-
1
MHz, CDCl
3
) δ – 60.2; IR (thin film, cm ) 2941, 2842, 1740, 1606, 1581, 1511, 1461, 1350,
+
1
253, 1164, 1130, 1042, 835, 752; HRMS (ESI) calcd for C29
27
H F
3
INO
5
S [M+H] : 686.0679,
found: 686.0673.
CF3
TsN
O
O
MeO
I
(Z)-(2-methoxyphenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)met
1
hyl 2-iodobenzoate (3e) : 74% yield, white solid. Mp = 70-72 ℃. H NMR (400 MHz,
CDCl
.6 Hz, 1H), 3.83 (s, 3H), 4.01-4.06 (m, 2H), 6.90-6.97 (m, 2H), 7.13-7.17 (m, 1H), 7.34-7.40
m, 4H), 7.46 (dd, J = 7.6 Hz, J = 1.6 Hz, 1H), 7.71 (d, J = 8.4 Hz, 2H), 7.75 (dd, J = 7.6 Hz,
= 1.6 Hz, 1H), 7.98 (dd, J = 8.0 Hz, J = 0.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ
3
) δ 1.17 (s, 3H), 2.01-2.31 (m, 2H), 2.44 (s, 3H), 3.15 (d, J = 9.6 Hz, 1H), 3.31 (d, J =
9
(
1
2
1
1
3
J
2
1
2
3
163.5, 157.5, 144.0, 141.5, 139.1, 134.3, 133.6, 133.1, 132.0, 131.6, 131.4, 129.8, 127.9,
S17

1
9
1
27.9, 126.0 (q, J = 277.0 Hz), 121.6, 120.2, 110.9, 94.4, 59.2, 55.4, 50.0, 41.5, 21.5; F
-
1
NMR (376 MHz, CDCl
3
) δ – 60.3; IR (thin film, cm ) 2942, 2840, 1740, 1646, 1599, 1461,
+
1
351, 1260, 1164, 1128, 1044, 815, 758; HRMS (ESI) calcd for C29
H
27
F
3
INO
5
S [M+H] :
686.0679, found: 686.0676.
(Z)-(2-fluorophenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methyl
1
2
1
1
-iodobenzoate (3f) : 75% yield, white solid. Mp = 64-66 ℃. H NMR (400 MHz, CDCl
3
) δ
.19 (s, 3H), 1.99-2.32 (m, 2H), 2.45 (s, 3H), 3.15 (d, J = 9.6 Hz, 1H), 3.34 (d, J = 9.6 Hz,
H), 3.99 (d, J = 14.8 Hz, 1H), 4.10 (d, J = 15.2 Hz, 1H), 7.12 (t, J = 8.8 Hz, 1H), 7.16-7.20
(
m, 2H), 7.35-7.45 (m, 4H), 7.52-7.56 (m, 1H), 7.71 (d, J = 8.0 Hz, 2H), 7.79 (dd, J
1
= 8.0 Hz,
= 0.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ
63.4, 160.1 (d, J = 248.0 Hz), 144.2, 141.7, 136.3, 136.1, 133.5, 133.0, 132.2 (d, J = 8.0 Hz),
1
3
J
2
= 1.6 Hz, 1H), 8.01 (dd, J
1
= 8.0 Hz, J
2
3
1
1
1
31.8, 131.6, 129.9, 128.0, 127.9, 125.8 (q, J = 277.0 Hz), 124.1 (d, J = 3.5 Hz), 120.8 (d, J =
5.8 Hz), 116.0 (d, J = 21.3 Hz), 94.5, 59.2 (d, J = 2.0 Hz), 50.1, 41.7 (d, J = 1.1 Hz), 40.1 (q,
19
-1
3
J = 27.0 Hz), 23.0, 21.5; F NMR (376 MHz, CDCl ) δ – 60.3, -111.2; IR (thin film, cm )
2923, 2851, 1743, 1612, 1581, 1431, 1351, 1262, 1234, 1164, 1130, 1044, 815, 742; HRMS
+
24
(ESI) calcd for C28H F
4
INO
4
S [M+H] : 674.0480, found: 674.0486.
(Z)-(4-fluorophenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methyl
1
2
-iodobenzoate (3g) : 75% yield, white solid. Mp = 66-68 ℃. H NMR (400 MHz, CDCl
3
) δ
S18

1
.23 (s, 3H), 1.93-2.25 (m, 2H), 2.45 (s, 3H), 3.19 (d, J = 9.6 Hz, 1H), 3.27 (d, J = 9.6 Hz,
H), 3.92 (d, J = 14.4 Hz, 1H), 4.09 (d, J = 14.8 Hz, 1H), 7.09 (t, J = 8.4 Hz, 2H), 7.18-7.22
1
(
m, 1H), 7.35-7.46 (m, 5H), 7.71 (d, J = 8.0 Hz, 2H), 7.75 (dd, J
1
= 7.6 Hz, J
) δ 163.5, 163.2 (d, J = 249.0 Hz),
44.2, 141.7, 141.0, 134.3, 133.5, 133.2, 132.3 (d, J = 9.0 Hz), 131.8, 131.4, 129.9, 129.2 (d,
2
= 1.6 Hz, 1H),
13
8
.02 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl
3
1
J = 4.0 Hz), 128.1, 128.0, 125.7 (q, J = 276.9 Hz), 115.7 (d, J = 21.7 Hz), 94.5, 59.4, 50.2,
1
9
4
3
1.6, 40.7 (q, J = 27.2 Hz), 24.3, 21.6; F NMR (376 MHz, CDCl ) δ – 60.3, -109.7; IR (thin
-1
film, cm ) 2923, 2851, 1741, 1600, 1508, 1461, 1351, 1261, 1234, 1163, 1131, 1043, 841,
+
7
43; HRMS (ESI) calcd for C28
H
24
F
4
INO
4
S [M+H] : 674.0480, found: 674.0487.
(Z)-(3-fluorophenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methyl
1
2
1
1
4
=
-iodobenzoate (3h) : 80% yield, white solid. Mp = 64-66 ℃. H NMR (400 MHz, CDCl
3
) δ
.26 (s, 3H), 1.99-2.24 (m, 2H), 2.45 (s, 3H), 3.20 (d, J = 9.6 Hz, 1H), 3.28 (d, J = 10.0 Hz,
H), 3.93 (d, J = 14.8 Hz, 1H), 4.09 (d, J = 14.8 Hz, 1H), 7.09-7.26 (m, 4H), 7.35-7.44 (m,
H), 7.71 (d, J = 8.4 Hz, 2H), 7.75 (dd, J
1
= 8.0 Hz, J
2 1 2
= 1.6 Hz, 1H), 8.02 (dd, J = 8.0 Hz, J
13
0.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ 163.4, 162.2 (d, J = 248.0 Hz), 144.2, 141.7,
3
1
40.4 (d, J = 2.0 Hz), 135.1, 135.0, 134.4, 133.5, 133.0, 131.7, 131.4, 130.2 (d, J = 8.0 Hz),
29.9, 128.1, 128.0, 126.0 (d, J = 3.0 Hz), 125.7 (q, J = 277.0 Hz), 117.2 (d, J = 21.8 Hz),
1
117.0 (d, J = 19.1 Hz), 94.5, 59.4 (d, J = 2.0 Hz), 50.2, 41.6, 40.6 (q, J = 27.4 Hz), 24.2, 21.5;
1
9
-1
F NMR (376 MHz, CDCl
3
) δ – 60.3, -111.3; IR (thin film, cm ) 2922, 2851, 1742, 1583,
1
460, 1431, 1351, 1262, 1164, 1133, 1044, 835, 771; HRMS (ESI) calcd for C28
24
H F
4
INO
4
S
+
[
M+H] : 674.0480, found: 674.0483.
S19

CF3
TsN
O
O
Cl
I
(Z)-(4-chlorophenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methy
1
l 2-iodobenzoate (3i) : 78% yield, white solid. Mp = 75-77 ℃. H NMR (400 MHz, CDCl
3
)
δ 1.23 (s, 3H), 1.93-2.27 (m, 2H), 2.45 (s, 3H), 3.18 (d, J = 9.6 Hz, 1H), 3.28 (d, J = 9.6 Hz,
1
7
=
H), 3.92 (d, J = 14.8 Hz, 1H), 4.08 (d, J = 14.8 Hz, 1H), 7.17-7.22 (m, 1H), 7.35-7.43 (m,
H), 7.70 (d, J = 8.0 Hz, 2H), 7.75 (dd, J
1
= 8.0 Hz, J
0.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ 163.4, 144.1, 141.7, 140.8, 136.0, 134.4, 133.5,
33.1, 131.7, 131.6, 131.6, 131.4, 129.9, 128.8, 128.0, 128.0, 125.7 (q, J = 277.0 Hz), 94.5,
2 1 2
= 2.0 Hz, 1H), 8.01 (dd, J = 7.6 Hz, J
13
3
1
5
19
9.4 (d, J = 2.0 Hz), 50.2, 41.6 (d, J = 1.1 Hz), 40.7 (q, J = 27.3 Hz), 24.3, 21.5; F NMR
-
1
(
376 MHz, CDCl
3
) δ – 60.2; IR (thin film, cm ) 2925, 2852, 1742, 1595, 1462, 1351, 1261,
+
1
236, 1164, 1134, 1092, 1044, 833, 752; HRMS (ESI) calcd for C28
3
H24ClF INO
4
S [M+H] :
690.0184, found: 690.0184.
CF3
TsN
O
O
COOMe
I
(Z)-(4-(methoxycarbonyl)phenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-yl
1
idene)methyl 2-iodobenzoate (3j) : 73% yield, white solid. Mp = 158-160 ℃. H NMR (400
MHz, CDCl
J = 9.6 Hz, 1H) , 3.92 (s, 3H), 3.95 (d, J = 15.2 Hz, 1H), 4.11 (d, J = 14.8 Hz, 1H), 7.18-7.22
m, 1H), 7.36 (d, J = 8.0 Hz, 2H), 7.40-7.44 (m, 1H), 7.54 (d, J = 8.4 Hz, 2H), 7.71 (d, J = 8.4
3
) δ 1.24 (s, 3H), 1.94-2.30 (m, 2H), 2.46 (s, 3H), 3.18 (d, J = 9.6 Hz, 1H), 3.28 (d,
(
Hz, 2H), 7.75 (dd, J
1
= 8.0 Hz, J
2
1 2
= 1.6 Hz, 1H), 8.02 (dd, J = 7.6 Hz, J = 0.8 Hz, 1H), 8.07
1
3
(
d, J= 8.4 Hz, 2H); C NMR (100 MHz, CDCl
3
) δ 166.1, 163.4, 144.2, 141.7, 140.8, 137.6,
S20

134.5, 133.5, 133.0, 131.7, 131.4, 131.3, 130.2, 129.9, 129.7, 128.1, 128.0, 125.7 (q, J =
1
9
2
77.0 Hz), 94.5, 59.4, 52.3, 50.2, 41.6 (d, J = 1.1 Hz), 40.6 (q, J = 27.3 Hz), 24.2, 21.5; F
-
1
NMR (376 MHz, CDCl
3
) δ – 60.3; IR (thin film, cm ) 2951, 2840, 1725, 1582, 1461, 1435,
1
351, 1281, 1236, 1164, 1133, 1044, 816, 755; HRMS (ESI) calcd for C30
27
H F
3
INO
6
S
+
[
M+H] : 714.0629, found: 714.0629.
CF3
TsN
O
O
NC
I
(
Z)-(2-cyanophenyl)(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methyl
1
2
1
4
7
3
-iodobenzoate (3k) : 62% yield, white solid. Mp = 80-82 ℃. H NMR (400 MHz, CDCl ) δ
.21 (s, 3H), 1.93-2.33 (m, 2H), 2.47 (s, 3H), 3.16-3.34 (m, 2H), 4.00 (d, J = 15.2 Hz, 1H),
.11 (d, J = 14.8 Hz, 1H), 7.20-7.24 (m, 1H), 7.38 (d, J = 8.0 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1H),
.54-7.57 (m, 1H), 7.67-7.78 (m, 5H), 7.96 (dd, J
1
= 7.6 Hz, J
) δ 163.1, 144.3, 142.0, 138.1, 137.3, 136.4, 133.8,
33.3, 132.9, 132.7, 132.1, 131.9, 131.6, 130.4, 130.0, 128.3, 127.9, 125.5 (q, J = 277.3 Hz),
2
= 1.2 Hz, 1H), 8.04 (d, J = 8.0
13
Hz, 1H); C NMR (100 MHz, CDCl
3
1
1
9
1
3
17.0, 113.4, 95.0, 59.2, 50.1, 41.8, 40.5 (m), 21.6; F NMR (376 MHz, CDCl ) δ – 60.3; IR
-1
(thin film, cm ) 2941, 2846, 2230, 1744, 1596, 1461, 1431, 1351, 1234, 1164, 1134, 1044,
+
8
15, 758; HRMS (ESI) calcd for C29
24
H F
3
IN
2
O
4
S [M+NH
4
] : 698.0792, found: 698.0800.
(
E)-(3-methyl-1-tosyl-3-(2,2,2-trifluoroethyl)piperidin-4-ylidene)(phenyl)methyl
1
2
0
1
-iodobenzoate (3l) : 78% yield, white solid. Mp = 68-70 ℃. H NMR (400 MHz, CDCl
.79 (s, 3H), 2.08-2.20 (m, 1H), 2.29 (d, J = 11.6 Hz, 1H), 2.42-2.53 (m, 5H), 2.74-2.79 (m,
H), 3.10-3.17 (m, 1H), 3.43 (dd, J = 12.0 Hz, J = 1.6 Hz, 1H), 3.88-3.89 (m, 1H), 7.11-7.15
= 8.0 Hz,
) δ 164.1, 143.9, 143.1,
41.4, 135.9, 133.8, 133.1, 131.2, 130.4, 129.9, 128.9, 128.3, 127.9, 127.7, 127.4, 126.5 (q, J
3
) δ
1
2
(
m, 1H), 7.30-7.36 (m, 6H), 7.41-7.43 (m, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.68 (dd, J
1
1
3
J
2 3
= 1.6 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl
1
S21

1
9
=
276.5 Hz), 94.3, 58.5, 46.7, 40.5 (q, J = 26.3 Hz) , 25.4, 25.2, 21.5 (d, J = 7.8 Hz); F
-1
NMR (376 MHz, CDCl
3
) δ – 60.0; IR (thin film, cm ) 2925, 2851, 1738, 1582, 1465, 1431,
INO
1360, 1281, 1236, 1165, 1105, 1044, 816, 756; HRMS (ESI) calcd for C29
27
H F
3
4
S
+
[M+H] : 670.0730, found: 670.0744.
CF3
TsN
O
O
S
I
(
Z)-(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(thiophen-2-yl)methyl
1
2
3
-iodobenzoate (3m) : 73% yield, white solid. Mp = 58-60 ℃. H NMR (400 MHz, CDCl )
δ 1.35 (s, 3H), 2.13-2.33 (m, 2H), 2.44 (s, 3H), 3.24 (s, 2H), 3.86 (d, J = 15.2 Hz, 1H), 4.11 (d,
J = 15.2 Hz, 1H), 7.01-7.04 (m, 1H), 7.18-7.22 (m, 2H), 7.34-7.43 (m, 4H), 7.69 (d, J = 8.0
1
3
Hz, 2H), 7.78 (dd, J
MHz, CDCl ) δ 163.6, 144.2, 141.7, 137.8, 134.9, 133.5, 133.1, 133.0, 131.6, 131.4, 130.9,
29.9, 128.7, 128.1, 128.0, 126.8, 125.9 (q, J = 276.9 Hz), 94.5, 59.6, 50.5, 41.9, 40.0 (q, J =
1 2
= 8.0 Hz, J = 1.6 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H); C NMR (100
3
1
2
1
1
9
-1
3
6.8 Hz), 23.9, 21.5; F NMR (376 MHz, CDCl ) δ – 60.2; IR (thin film, cm ) 2944, 2852,
742, 1582, 1461, 1430, 1351, 1261, 1236, 1164, 1133, 1094, 1082, 1042, 815, 743; HRMS
+
(ESI) calcd for C26
H
23
F
3
INO
4
S
2
[M+H] : 662.0138, found: 662.0139.
(
Z)-(4-methyl-4-(2,2,2-trifluoroethyl)dihydrofuran-3(2H)-ylidene)(phenyl)methyl
1
2
2
2
-iodobenzoate (3n) : 69% yield, colorless liquid. H NMR (400 MHz, CDCl
.00-2.31 (m, 2H), 3.75 (d, J = 9.2 Hz, 1H), 3.92 (d, J = 8.8 Hz, 1H), 4.61 (q, J = 14.4 Hz,
H), 7.13-7.17 (m, 1H), 7.36-7.43 (m, 4H), 7.51-7.54 (m, 2H), 7.78 (dd, J = 8.0 Hz, J = 1.6
) δ 163.8, 141.6, 139.9, 136.8,
33.7, 133.6, 133.2, 131.2, 130.1, 129.6, 128.4, 127.9, 126.2 (q, J = 276.9 Hz), 94.4, 79.6,
3
) δ 1.27 (s, 3H),
1
2
13
Hz, 1H), 7.99 (d, J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl
3
1
7
1
9
3
0.3, 42.2 (d, J = 1.3 Hz), 40.0 (q, J = 27.2 Hz), 23.4; F NMR (376 MHz, CDCl ) δ – 60.6;
-1
IR (thin film, cm ) 2925, 2840, 1744, 1660, 1582, 1461, 1431, 1360, 1371, 1260, 1234, 1132,
+
1
077, 1047, 767, 740; HRMS (ESI) calcd for C21
18
H F
3
INO
3
[M+NH
4
] : 520.0591, found:
520.0596.
S22

CF3
O
O
O
I
(
Z)-(4-methyl-4-(2,2,2-trifluoroethyl)dihydrofuran-3(2H)-ylidene)(p-tolyl)methyl
1
2
-iodobenzoate (3o) : 68% yield, colorless liquid. H NMR (400 MHz, CDCl
.04-2.31 (m, 2H), 2.38 (s, 3H), 3.75 (d, J = 9.2 Hz, 1H), 3.91 (d, J = 8.8 Hz, 1H), 4.59 (q, J =
4.0 Hz, 2H), 7.13-7.17 (m, 1H), 7.22 (d, J = 8.0 Hz, 2H), 7.36-7.41 (m, 3H), 7.70 (dd, J
3
) δ 1.27 (s, 3H),
2
1
1
=
13
7
.6 Hz, J
2 3
= 1.6 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl ) δ 163.8,
1
41.6, 140.1, 139.6, 136.6, 133.9, 133.1, 131.2, 130.7, 130.0, 129.1, 127.9, 126.3 (q, J =
1
9
277.0 Hz), 94.4, 79.7, 70.3, 42.2, 40.1 (q, J = 27.2 Hz), 23.4, 21.4; F NMR (376 MHz,
-
1
CDCl
3
) δ – 60.5; IR (thin film, cm ) 2944, 2853, 1742, 1610, 1583, 1462, 1431, 1371, 1290,
+
1
5
261, 1236, 1134, 1079, 1046, 822, 741; HRMS (ESI) calcd for C22
20
H F
3
INO
3
4
[M+NH ] :
34.0747, found: 534.0745.
(
Z)-(4-(methoxycarbonyl)phenyl)(4-methyl-4-(2,2,2-trifluoroethyl)dihydrofuran-3(2H)-y
1
lidene)methyl 2-iodobenzoate (3p) : 60% yield, colorless liquid. H NMR (400 MHz, CDCl
3
)
δ 1.26 (s, 3H), 1.99-2.33 (m, 2H), 3.75 (d, J = 9.2 Hz, 1H), 3.93-3.95 (m, 4H), 4.63 (q, J =
1
1
4.4 Hz, 2H), 7.15-7.20 (m, 1H), 7.38-7.42 (m, 1H), 7.62 (d, J = 8.4 Hz, 2H), 7.78 (dd, J =
1
3
8
2
.0 Hz, J = 1.6 Hz, 1H), 7.99-8.01 (m, 1H), 8.11 (d, J = 8.4 Hz, 2H); C NMR (100 MHz,
CDCl
3
) δ 166.3, 163.7, 141.7, 138.8, 138.0, 137.8, 133.5, 133.3, 131.2, 131.1, 130.2, 129.7,
19
128.0, 126.0 (q, J = 277.0 Hz), 94.4, 79.6, 70.4, 52.3, 42.3, 40.1 (q, J = 27.2 Hz), 23.3; F
-1
NMR (376 MHz, CDCl
3
) δ – 60.5; IR (thin film, cm ) 2952, 2851, 1726, 1609, 1583, 1461,
1
435, 1372, 1281, 1256, 1236, 1134, 1078, 1047, 776, 742; HRMS (ESI) calcd for
+
C
23 20
H F
3
INO
5
4
[M+NH ] : 578.0646, found: 578.0649.
S23

(
E)-(3-methyl-3-(2,2,2-trifluoroethyl)dihydro-2H-pyran-4(3H)-ylidene)(phenyl)methyl
1
2
-iodobenzoate (3q) : 67% yield, white solid. Mp = 114-116 ℃. H NMR (400 MHz, CDCl
3
)
δ 0.68 (s, 3H), 2.12-2.24 (m, 1H), 2.39-2.47 (m, 1H), 2.60 (d, J = 14.8 Hz, 1H), 2.93-3.00 (m,
1
H), 3.29 (d, J = 11.6 Hz, 1H), 3.53 (d, J = 11.2 Hz, 1H), 3.57-3.64 (m, 1H), 4.06-4.10 (m,
H), 7.10-7.14 (m, 1H), 7.33-7.36 (m, 4H), 7.49-7.52 (m, 2H), 7.72 (dd, J = 8.0 Hz, J = 1.6
) δ 164.1, 142.2, 141.5, 136.4,
34.2, 132.9, 131.2, 130.7, 129.5, 128.8, 127.9, 127.8, 126.8 (q, J = 276.7 Hz), 94.4, 78.2,
1
1
2
13
Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H); C NMR (100 MHz, CDCl
3
1
6
19
3
8.7, 40.1 (q, J = 26.3 Hz), 37.9, 26.1, 23.1; F NMR (376 MHz, CDCl ) δ – 60.0; IR (thin
-1
film, cm ) 2943, 2853, 1739, 1582, 1465, 1431, 1367, 1260, 1176, 1135, 1105, 1044, 771,
+
741; HRMS (ESI) calcd for C22
20
H F
3
INO
3
[M+NH
4
] : 534.0747, found: 534.0751.
(E)-diethyl
4
-(((2-iodobenzoyl)oxy)(phenyl)methylene)-3-methyl-3-(2,2,2-trifluoroethyl)cyclopentan
1
e-1,1-dicarboxylate (3r) : 82% yield, colorless liquid. H NMR (400 MHz, CDCl
3
) δ 1.19 (s,
H), 1.23-1.30 (m, 6H), 1.99-2.21 (m, 2H), 2.51 (d, J = 14.4 Hz, 1H), 2.74 (d, J = 14.4 Hz,
H), 3.17 (d, J = 18.0 Hz, 1H), 3.41 (dd, J = 18.0 Hz, J = 0.8 Hz, 1H), 4.17-4.27 (m, 4H),
.11-7.16 (m, 1H), 7.35-7.39 (m, 4H), 7.48-7.51 (m, 2H), 7.84 (dd, J = 8.0 Hz, J = 1.6 Hz,
= 0.8 Hz, 1H); C NMR (100 MHz, CDCl ) δ 171.5, 171.4,
63.5, 141.7, 141.6, 137.6, 134.1, 133.8, 133.0, 131.4, 130.6, 129.3, 128.3, 127.9, 126.3 (q, J
277.5 Hz), 94.5, 61.9, 61.8, 57.3, 46.6, 42.9 (q, J = 26.3 Hz), 41.7, 37.6, 21.3, 14.0, 13.9;
3
1
7
1
1
1
2
1
2
1
3
H), 7.98 (dd, J
1
= 7.6 Hz, J
2
3
=
1
9
-1
F NMR (376 MHz, CDCl
3
) δ – 59.7; IR (thin film, cm ) 2930, 2896, 1734, 1582, 1464,
INO
6
1
430, 1368, 1260, 1230, 1187, 1140, 1043, 773, 741; HRMS (ESI) calcd for C28
28
H F
3
+
4
[M+NH ] : 662.1221, found: 662.1225.
S24

(
Z)-(4-methyl-5-oxo-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(phenyl)methyl
1
2
-iodobenzoate (3s) : 60% yield, white solid. Mp = 168-170 ℃. H NMR (400 MHz, CDCl
3
)
δ 1.22 (s, 3H), 1.97-2.08 (m, 1H), 2.37-2.46 (m, 4H), 4.51 (d, J = 14.8 Hz, 1H), 4.77 (d, J =
1
4.4 Hz, 1H), 7.18-7.22 (m, 1H), 7.34 (d, J = 8.4 Hz, 2H), 7.40-7.45 (m, 4H), 7.51-7.54 (m,
H), 7.86 (dd, J = 7.6 Hz, J = 1.2 Hz, 1H), 7.93 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.0 Hz, 1H);
C NMR (100 MHz, CDCl ) δ 173.9, 163.2, 145.6, 145.2, 141.8, 133.9, 133.5, 133.0, 132.8,
31.6, 130.1, 130.0, 129.6, 128.4, 128.3, 128.1, 124.8 (q, J = 277.1 Hz), 123.0, 94.6, 47.8,
2
1
2
1
3
3
1
4
1
9
3
4.7 (d, J = 2.1 Hz), 41.3 (q, J = 27.5 Hz), 26.1, 21.7; F NMR (376 MHz, CDCl ) δ – 62.0;
-1
IR (thin film, cm ) 2923, 2874, 1742, 1597, 1576, 1466, 1430, 1364, 1262, 1237, 1173, 1131,
+
814, 753; HRMS (ESI) calcd for C28
23
H F
3
INO
5
S [M+H] : 670.0366, found: 670.0377.
(
Z)-(4-methyl-5-oxo-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(p-tolyl)methyl
1
2
1
1
7
-iodobenzoate (3t) : 62% yield, white solid. Mp = 78-80 ℃. H NMR (400 MHz, CDCl
.23 (s, 3H), 1.99-2.11 (m, 1H), 2.36 (s, 3H), 2.39-2.43 (m, 1H), 2.44 (s, 3H), 4.50 (d, J =
4.8 Hz, 1H), 4.75 (d, J = 14.4 Hz, 1H), 7.17-7.21 (m, 3H), 7.34 (d, J = 8.0 Hz, 2H),
3
) δ
.39-7.45 (m, 3H), 7.85 (dd, J
1
= 7.6 Hz, J
2
= 1.6 Hz, 1H), 7.93 (d, J = 8.4 Hz, 2H), 8.02 (dd,
= 1.2 Hz, 1H); C NMR (100 MHz, CDCl ) δ 174.0, 163.2, 145.6, 145.3,
41.8, 140.1, 140.0, 133.5, 133.1, 131.6, 130.0, 129.9, 129.6, 129.1, 128.3, 128.0, 127.5,
24.8 (q, J = 277.0 Hz), 122.8, 94.6, 47.8, 44.7 (d, J = 2.1 Hz), 41.2 (q, J = 27.4 Hz), 26.2,
1
3
J
1
1
2
1
1
= 8.0 Hz, J
2
3
19
-1
1.7, 21.3; F NMR (376 MHz, CDCl
3
) δ – 62.0; IR (thin film, cm ) 2926, 2880, 1741, 1598,
582, 1455, 1430, 1363, 1262, 1237, 1173, 1130, 877, 819, 745; HRMS (ESI) calcd for
+
C
29 25
H F
3
INO
5
S [M+H] : 684.0523, found: 684.0529.
S25

(
Z)-(4-(methoxycarbonyl)phenyl)(4-methyl-5-oxo-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolid
1
in-3-ylidene)methyl 2-iodobenzoate (3u) : 58% yield, white solid. Mp = 88-90 ℃. H NMR
400 MHz, CDCl ) δ 1.22 (s, 3H), 1.92-2.04 (m, 1H), 2.41-2.47 (m, 4H), 3.93 (s, 3H), 4.52 (d,
J = 14.8 Hz, 1H), 4.78 (d, J = 14.8 Hz, 1H), 7.20-7.24 (m, 1H), 7.35 (d, J = 8.4 Hz, 2H),
.43-7.47 (m, 1H), 7.62 (d, J = 8.4 Hz, 2H), 7.86 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.93 (d, J
8.4 Hz, 2H), 8.03 (dd, J = 8.0 Hz, J = 0.8 Hz, 1H), 8.09 (d, J = 8.0 Hz, 2H); C NMR
100 MHz, CDCl ) δ 173.7, 166.2, 163.3, 145.8, 144.2, 141.9, 137.3, 134.0, 133.8, 132.9,
31.6, 130.3, 129.7, 129.7, 128.4, 128.2, 124.8 (q, J = 277.0 Hz), 124.1, 94.7, 52.5, 47.8, 44.8
(
3
7
1
2
1
3
=
1
2
(
3
1
1
9
3
(d, J = 2.1 Hz), 41.4 (q, J = 27.5 Hz), 26.2, 21.8; F NMR (376 MHz, CDCl ) δ – 62.1; IR
-1
(thin film, cm ) 2926, 2880, 1741, 1598, 1582, 1455, 1430, 1363, 1262, 1237, 1173, 1130,
+
875, 819, 745; HRMS (ESI) calcd for C30
25
H F
3
INO
7
S [M+H] : 728.0421, found: 728.0416.
.
(Z)-phenyl(4-phenyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)methyl
1
2
2
4
7
-iodobenzoate (3y) : 70% yield, white solid. Mp = 58-60 ℃. H NMR (400 MHz, CDCl
3
) δ
.41-2.53 (m, 4H), 2.58-2.70 (m, 1H), 3.56 (d, J = 10.0 Hz, 1H), 3.83 (d, J = 10.0 Hz, 1H),
.13 (d, J = 14.4 Hz, 1H), 4.26 (d, J = 14.8 Hz, 1H), 7.12-7.19 (m, 5H), 7.24-7.42 (m, 9H),
1
3
.63 (d, J = 8.0 Hz, 2H), 7.78 (dd, J
) δ 163.6, 143.9, 142.9 (d, J = 6.0 Hz), 141.6, 133.5, 133.3, 132.9,
32.2, 131.9, 131.4, 129.7, 129.6, 129.4, 128.6, 128.0, 128.0, 127.8, 127.4, 126.4, 125.5 (q, J
1 2
= 7.6 Hz, J = 1.6 Hz, 1H), 8.00 (d, J = 7.6 Hz, 1H); C
NMR (100 MHz, CDCl
3
1
1
9
=
3
277.4 Hz), 94.3, 59.8, 50.8, 48.9, 39.2 (q, J = 27.4 Hz), 21.5; F NMR (376 MHz, CDCl )
-1
δ – 58.4; IR (thin film, cm ) 3059, 3025, 2921, 2854, 1741, 1581, 1495, 1439, 1351, 1258,
+
1
27 3 4
234, 1160, 1128, 1041, 813, 743; HRMS m/z calcd for C33H F INO S [M+H] : 718.0730,
found: 718.0730.
S26

(Z)-(4-methyl-1-tosyl-4-(2,2,2-trifluoroethyl)pyrrolidin-3-ylidene)(phenyl)methyl
1
4
-chlorobenzoate (5) : white solid. Mp = 146-148 ℃. H NMR (400 MHz, CDCl
3
) δ 1.24 (s,
3H), 1.94-2.18 (m, 2H), 2.47 (s, 3H), 3.22 (q, J = 9.6 Hz, 2H), 3.86 (d, J = 14.8 Hz, 1H), 4.06
(d, J = 14.8 Hz, 1H), 7.35-7.44 (m, 9H), 7.69 (d, J = 8.4 Hz, 2H), 7.93 (d, J = 8.8 Hz, 2H);
1
3
3
C NMR (100 MHz, CDCl ) δ 163.0, 144.1, 142.1, 140.4, 133.4, 133.4, 132.1, 131.3, 130.0,
1
2
1
29.8, 129.8, 129.0, 128.5, 127.9, 127.3, 125.8 (d, J = 277.0 Hz), 59.5, 49.9, 41.5, 40.6 (q, J =
19
-1
3
7.0 Hz), 24.4, 21.6; F NMR (376 MHz, CDCl ) δ – 60.3; IR (thin film, cm ) 2924, 2851,
734, 1595, 1487, 1451, 1351, 1250, 1164, 1088, 817, 755; HRMS (ESI) calcd for
+
C
28
H
25ClF
3
NO
4
S [M+H] : 564.1218, found: 564.1228.
6
. Reference:
[
1]. a) T. Kataoka, M. Yoshimatsu, Y. Noda, T. Sato, H. Shimizu, M. Hori, J. Chem. Soc.
Perkin Trans. 1 1993, 1, 121; b) A. Gansäuer, M. Otte, L. Shi, J. Am. Chem. Soc. 2011, 133,
16.
4
[2]. N. Dieltiens, K.Moonen, C. V. Stevens, Chem. Eur. J. 2007, 13, 203.
[3]. a) S. I. Lee, S. Y. Park, J. H. Park, I. G. Jung, S. Y. Choi, Y. K. Chung, B. Y. Lee, J. Org.
Chem. 2006, 71, 91; b) P. Garcia, Y. Evanno, P. George, M. Sevrin, G. Ricci, M. Malacria, C.
Aubert, V. Gandon, Org. Lett. 2011, 13 , 2030.
[4]. F. Y. Kwong, H. W. Lee, L. Qiu, W. H. Lam, Y. M. Li, H. L. Kwong, A. S. C. Chan, Adv.
Synth. Catal. 2005, 347, 1750.
[5]. Enyne 1q was prepared in the same with 1p.
[6]. a) T. Kobayashi, Y. Koga, K. Narasaka, J. Organomet. Chem. 2001, 624, 73; b) M.
Tokuda, H. Fujita, M. Nitta, H. Suginome, Heterocycles 1996, 42, 385.
[7]. S. Arai, Y. Koike and A. Nishida, Adv. Synth. Catal. 2010, 352, 893.
[8]. K. T. Sylvester, P. J. Chirik, J. Am. Chem. Soc. 2009, 131, 8772.
[9]. M. Lemhadri, H. Doucet, M. Santelli, Synthesis 2005, 1359.
S27

7
. Mechanistic experiment: Reaction of 1a in the presence of TEMPO:
,6- Enyne (1a) (0.068 g, 0.2 mmol) and TEMPO (62.4mg, 0.40 mmol) were dissolved in 2
mL of DCM. Togni’s reagent (2) (0.126 g, 0.4 mmol) and CuPF (CH CN) (15 mg, 0.04
1
6
3
4
mmol) were successively added to this solution and the resulting mixture was stirred at 50 °C
for 20 hours. 3a was obtained at the isolated yield of 36%.The TEMPO-CF3 adduct was
+
19
formed in 12% yield (based on starting TEMPO): MS (EI, m/z): 225 [M] . F NMR (376
MHz, CDCl ) δ -55.7.
3
S28

8. Crystallographic data of 3a:
CF3
TsN
O
O
I
3a
Bond precision:
Cell: a=11.3250(4) b=29.3993(13) c=9.7380(4)
alpha=90 beta=94.861(3) gamma=90
C-C = 0.0086 A
Wavelength=0.71070
Temperature:193 K
Calculated
Reported
3230.6(2)
P 1 21/c 1
-P 2ybc
Volume
3230.6(2)
P 21/c
Space group
Hall group
Moiety formula
Sum formula
Mr
-P 2ybc
C28 H25 F3 I N O4 S
C28 H25 F3 I N O4 S
655.46
C28 H25 F3 I N O4 S
C28 H25 F3 I N O4 S
655.45
Dx,g cm-3
Z
1.348
1.348
4
4
Mu (mm-1)
F000
1.102
1.102
1312.0
1312.0
F000'
1311.26
h,k,lmax
Nref
14,36,12
6601
14,36,12
6591
Tmin,Tmax
Tmin'
0.842,0.886
0.759
0.911,1.000
Correction method= MULTI-SCAN
Data completeness= 0.998
Theta(max)= 26.370
wR2(reflections)= 0.2120( 6591)
R(reflections)= 0.0672( 3684)
S = 1.027
Npar= 345
S29