Metal-Free Difluoromethylselenolation of Arylamines under Visible-Light Photocatalysis

Article abstract of DOI:10.1021/acs.joc.9b02535

A novel visible-light photocatalytic difluoromethylselenolation of aryl amines via in situ generation of aryldiazonium salts was achieved using Se-(difluoromethyl) 4-methylbenzenesulfonoselenoate, which was synthesized for the first time. The reagent is readily accessible and shelf-stable. The metal-free reaction conditions and the broad substrate scope provide a green protocol for the efficient and rapid introduction of the difluoromethylselenylether group.

Full text of DOI:10.1021/acs.joc.9b02535

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Note
Metal-Free Difluoromethylselenolation of
Arylamines Under Visible-light Photocatalysis
Kui Lu, Quan Li, Xiaolan Xi, Ting Zhou, and Xia Zhao
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b02535 • Publication Date (Web): 08 Dec 2019
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Metal-Free Difluoromethylselenolation of Arylamines Under
Visible-light Photocatalysis
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Kui Lu,†,* Quan Li, † Xiaolan Xi,† Ting Zhou,† and Xia Zhao‡,*
†China International Science and Technology Cooperation Base of Food Nutrition/Safety
and Medicinal Chemistry, College of Biotechnology, Tianjin University of Science &
Technology, Tianjin, China, 300457
‡College of Chemistry, Tianjin Key Laboratory of Structure and Performance for
Functional Molecules, Key laboratory of Inorganic-organic Hybrid Functional Material
Chemistry, Ministry of Education, Tianjin Normal University, Tianjin, China, 300387
E-mail: lukui@tust.edu.cn; hxxyzhx@mail.tjnu.edu.cn;
TsSeCF2H
p-TsOH, t-BuONO
24 examples
42%-80% yields
Ar SeCF2H
Ar NH2
Rose Bengal
White LEDs
Abstract: A novel visible-light photocatalytic difluoromethylselenolation of aryl
amines via in situ generation of aryldiazonium salts was achieved using
Se-(difluoromethyl) 4-methylbenzenesulfonoselenoate, which was synthesized for the
first time. The reagent is readily accessible and shelf-stable. The metal-free reaction
conditions and the broad substrate scope provide a green protocol for the efficient and
rapid introduction of the difluoromethylselenylether group.
Trifluoromethyl and difluoromethylchalcogen groups have attracted widespread
attention in academia and industry over the past decade due to their unique
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physicochemical properties including high lipophilicity and good cell membrane
permeability.1 Significant progress has been made towards the development of methods
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that allow the direct incorporation of OCF3,2 OCF2H,3 SCF3 and SCF2H5 into organic
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molecules. The SeCF3 group has a high Hansch lipophilicity parameter value (πR = 1.29)
which falls between that of the CF3O and CF3S groups and has recently gained significant
interest in organofluorine chemistry and drug design.6 More recently, strategies for
incorporation of the related SeCF2H group have attracted attention in the synthetic
community.7 However, direct SeCF2H incorporation using a shelf-stable reagent has been
rarely reported.8
Arylamines are inexpensive and widely available starting materials and are useful
handles for the introduction of boryl,9 phosphoryl,10 sulfenyl,11 stannyl,12 and
trifluoromethyl groups13
via Sandmeyer-type chemistry. In 2018, we reported a
visible-light mediated photocatalytic trifluoromethylthiolation of aryldiazonium salts and
arylamines using S-trifluoromethyl 4-methoxylbenzenesulfonothioate (TsSCF3)14.
Recently, Billard and Tlili group developed
a
visible-light mediated
trifluoromethylselenolation of aryldiazonium salts.15 We report herein, the preparation of
Se-(difluoromethyl) 4-methylbenzenesulfonoselenoate (1, TsSeCF2H) for the first time
(Scheme 1) and describe its use for the direct difluoromethylselenolation of arylamines
under visible-light photocatalysis.
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1) LiAlH4
(1)
ArSeSeAr
Ar SeCF2H
Ref. 7a
Ref. 7c
2) HCF2Cl/NaOH
ClCF2CO2Na
K2CO3
(2) PhSeH
(3) PhSeH
Ph SeCF2H
[Ph3P-CF2H] Br
NaH 365nm
TMSCF2H
Ph SeCF2H Ref. 7e
(4)
R SeCN
R
SeCF2H
Ref. 7f
t-BuOK
TsSeCF2H
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p-TsOH, t-BuONO
(5) Ar NH2
Ar SeCF2H
Ths work
Rose Bengal
White LEDs
SCHEME 1. Methods for SeCHF2 incorporation
We began with the synthesis of the difluoromethylselenolation reagent (1) using
KSeCN, benzyl bromide (BnBr), CF2HSiMe3, and sodium 4-toluenesulfinate (TsNa) in
three steps employing a protocol similar to the one used for the preparation of
Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate (Scheme 2)16.
TBAF
KSeCN
THF
TMSCF2H
BnSeCN
BnSeCF2H
Ref. 16
BnBr
THF
1) SOCl2 (1.0 eq.)
DCM, 0 o
C
TsSeCF2H
70%
BnSeCF2H
2) TsNa (1.1 eq.)
DCM -78 o
1
C
SCHEME 2. Preparation of reagent 1
With the reagent 1 in hand, we attempted the difluromethylselenolation of ethyl
4-aminobenzoate (2a) with 4-methylbenzenesulfonic acid (TsOH), tert-butyl nitrite (TBN)
and 1 in the presence of Rose Bengal (RB) under white light irradiation in dimethyl
sulfoxide (DMSO) at room temperature, based on our previously reported conditions14.
To our delight, the desired difluoromethylselenolation product 3a was obtained in 54%
yield (Table 1, entry 1). With the successful formation of 3a, we turned to the
optimisation of various reaction parameters to improve the reaction yield. While the use
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of DMF or THF as reaction solvent afforded 3a in a lower yield (Table 1, Entries 2 and
3), MeOH, water, or CH3CN furnished 3a only in trace quantities. An increase in the
reaction concentration of 2a from 0.20 M to 0.25 M, afforded an increase in yield from
75% to 80%, respectively. However, a further increase in the concentration of 2a to 0.30
M led to a diminished yield. Decreasing the photocatalyst loading to 5 mol% afforded the
product in a reduced 41 % yield, while the absence of TsOH from the reaction condition
furnished the product in 68% yield. The use of green light irradiation furnished 3a in a
much lowered 25% yield. Reactions carried out in the absence of the photocatalyst, or
light irradiation did not afford any product. Further, the extension of reaction time to 30 h
did not improve the yield.
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TABLE 1. Reaction Optimisationa
TsOH (1.2 eq)
SeCF2H
NH2
t-BuONO (1.2 eq)
O
S
Rose Bengal (8 mol%)
SeCF2H
+
White LED (5 W)
DMSO (1 mL)
R.T.
O
COOEt
COOEt
10h
3a
2a
0.2 mmol
1
(1.5 eq)
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Entry
Deviation from standard conditions
Yield (%)
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1
2
None
DMF instead of DMSO
THF instead of DMSO
MeOH instead of DMSO
H2O instead of DMSO
MeCN instead of DMSO
2a (0.25 M)
75
62
3
52
4
Trace
Trace
Trace
80
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2a (0.30 M)
72
9
Rose Bengal (5 mol%)
Without TsOH
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68
Green LED instead of White LED
No Rose Bengal
25
0
No light
0
30h
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a Reactions were performed with TsSeCF2H (0.3 mmol, 1.5 equiv.),
2a (0.2 mmol, 1 equiv.), TsOH (0.24mmol, 1.2 equiv.), t-BuONO
(0.24mmol, 1.2 equiv.) Rose Bengal (0.016 mmol, 8 mol% ), and
solvent (1 mL). The reaction mixture was stirred at rt for 10 hours.
With the optimised reaction conditions in hand, the generality of this reaction was
examined by employing a series of arylamines (2b–2r) as substrates, and the results are
summarised in Scheme 3. Anilines bearing both electron-donating and
electron-withdrawing substituents, as well as ortho-, meta- and para-substituted anilines
were compatible with the reaction conditions and afforded the corresponding
difluoromethylselenolation products (3b-3k) in moderate to good yields. Notably,
sterically hindered anilines 2l and 2m were smoothly transformed to the desired products
in 79 and 46% yields, respectively. Having evaluated sterics and electronics of aniline
substitutions, we studied the compatibility of other complex functionalities on the aniline
framework to the reaction conditions. The urea (2n), cyclic ketone (2s and 2t), acetal (2o),
cyclic imide (2p), lactone (2q), and α, β-unsaturated lactone (2r) functionalities, as well
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as aromatic heterocyclic amines (2u-2w) were compatible during this transformation and
furnished the desired products (3n-3w) in moderate to good yields.
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TsOH (1.2 eq)
t-BuONO (1.2 eq)
SeCF2H
SeCF2H
NH2
+
O
S
Rose Bengal (8 mol%)
R
R
SeCF2H
White LED (5 W)
DMSO (1 mL)
R.T.
O
2
1
(1.5 eq)
0.25 mmol
3
10h
SeCF2H
SeCF2H
O2N
SeCF2H
NC
EtOOC
3a
HOOC
3b
3c
3d
, 80%
SeCF2H
, 67%
SeCF2H
, 41%
, 53%
SeCF2H
SeCF2H
Ph
O
MeO
HO
O
NH2
3e,
3f,
3g,
3h,
3l,
73%
70%
62%
SeCF2H
69%
SeCF2H
SeCF2H
SeCF2H
Ph
Ph
OMe
3i,
3j,
3k,
72%
80%
76%
SeCF2H
79%
SeCF2H
O
H
N
SeCF2H
Et
SeCF2H
HN
O
O
Et
O
N
H
O
3p,
60%
3o,
48%
O
3n,
57%
3m,
46%
O
O
SeCF2H
O
HF2CSe
SeCF2H
SeCF2H
O
O
O
O
3r,
46%
3q,
47%
3t,
3s,
61%
59%
SeCF2H
SeCF2H
EtOOC
SeCF2H
S
N
O
N
3u,
3v,
3w,
51%
60%
49%
SCHEME 3. Substrate scope of the difluoromethylselenolation of arylamines
To further probe the relevance of the developed transformation to the preparation of
medicinally relevant molecules, we carried out the functionalization of known
biologically active scaffolds, and were pleased to find the successful incorporation of the
difluoromethylselenyl group into a clofibrate derivative (3aa), pomalidomide (3ab),
sulfamethoxazole (3ac), and L-menthol derivative (3ad) in moderate to good yields
(Scheme 4)
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SeCF2H
O
O
SeCF2H
HN
EtO
O
N
O
O
O
3aa
3ab
, 77%
, 44%
9
SeCF2H
SeCF2H
H
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O
N
N
S
O
O
O
O
3ac
, 48%
3ad
, 80%
a Reaction conditions: amine (0.25 mmol), (0.3 mmol), TsOH
(0.24mmol), t-BuONO (0.24mmol) Rose Bengal (0.016 mmol, 8 mol% ),
and DMSO(1 mL) under the irratdation under white light irradiation at r.t.
for 10 hours
1
SCHEME 4. Difluoromethylselenolation of bioactive molecules
To investigate the mechanism this reaction, we carried out a series of 19F NMR
experiments to examine the difluoromethylselenolation of 2a by 1 under the optimised
reaction condition with trifluoromethylbenzene as an internal standard (δ = -63.20 ppm).
The NMR spectrum acquired after 15 min revealed the presence of three fluorine peaks,
which were assigned to the desired product 3a (δ = -90.47 ppm), 1 (δ = -91.06 ppm), and
a unknown fluorine peak (δ = -88.59 ppm). The fluorine signal corresponding to 1 almost
dispappeared in the NMR spectrum acquired after 30 min, and the intensities of the
fluorine peaks of 3a and the unknown compound increased. After 1 hour, the fluorine
peak intensity of the unknown compound decreased and that of 3a increased. To explore
the structure of the unknown compound, we irradiate 1 under white light in the absence
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of 2a, the photocatalyst, and other additives. We found only two fluorine peaks by F
NMR, 1 (δ = -91.06 ppm)and the unknown compound (δ = -88.59 ppm), and it was
identified as 1,2-bis(difluoromethyl)diselane 6 (HCF2SeSeCF2H) by GC-MS (Scheme 5,
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Eq. a). Further, TsOH was detected by ESI-HRMS even when the reaction was carried
out in the absence of TsOH.
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Based on related mechanisms in the literature,14, 15 we suspected that aryl radicals
might be key intermediates in this transformation, and to probe their presence, two
radical trapping experiments were carried out (Scheme 5, Eq. b and Eq. c) under standard
reaction conditions. When 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO, 2 equiv) or 1,1-
diphenylethylene (2 equiv) was added to the reaction under the standard reaction
conditions, the yield of 3a decreased to 10% or 42% respectively. Furthermore, the
ESI-HRMS analysis of the reaction mixture indicated the formation of the TEMPO-arene
adduct (4a) and triarylethylene (5a), which confirmed the intermediacy of free radical
species in this reaction.
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TsSeCF2H
HF2CSe SeCF2H
detected by GC-MS
and 19F NMR
(a)
White LED
(5 W), 1h
6
1
NH2
SeCF2H
standard
N
O
condition
+
TsSeCF2H
TEMPO
(2.0 eq.)
detected by
HRMS (ESI)
1
(b)
COOEt
2a
COOEt
3a, 10%
4a
COOEt
Ph
NH2
SeCF2H
Ph
standard
TsSeCF2H condition
Ph
Ph
+
detected by
HRMS (ESI)
1
TEMPO
(2.0 eq.)
(c)
COOEt
COOEt
5a
2a
3a, 42%
COOEt
SCHEME 5. Investigations to elucidate the reaction mechanism
Based on the aforementioned results and related literature,17 a plausible mechanism for
the difluoromethylselenolation reaction is proposed (Scheme 6). The arylamine 2 reacts
with TsOH and TBN to form an arenediazonium salt 7. The photocatalyst Rose Bengal
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(RB) undergoes excitation under visible light irradiation to RB*, which through a single
electron transfer (SET) with arenediazonium salt 7 leads to the generation of RB·-and
aryl radical 8, which reacts with 1,2-bis(difluoromethyl)diselane 6 generated by the
homolysis of the reagent 1 under visible light to deliver the corresponding aryl
difluoromethylselenol ether 3 and difluoromethylselenol radical 9 which can
self-combine to form 6. Subsequently, the sulfone radical 10 undergoes a single electron
transfer (SET) with the radical anion of the photocatalyst (RB·-) which leads to the
formation of sulfite cation 11 along with the regeneration of the photocatalyst. The
reaction of the sulphite cation 11 with water affords TsOH (12).
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O
S
NH2
O
S
H2O
OH
R1
O
O
11
12
2
p-TsOH
t-BuONO
O
S
RB
SeCF2H
N2OTs
O
O
S
O
10
RB2-
R1
hv
-N2
7
hv
RB2-
*
R1
1
HF2CSe
HF2CSe SeCF2H
8
SeCF2H
9
6
R1
3
SCHEME 6. Plausible mechanism of Rose Bengal catalysed selenodifluoromethylation
Finally, the practical applications of this transformation were investigated. 6-mmol
scale difluoromethylselenolation reaction of 2j (Scheme 7) was carried out and the
desired product 3j was obtained in 64% yield.
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TsOH (7.2 mmol)
SeCF2H
Ph
NH2
O
S
O
1
t-BuONO (7.2 mmol)
SeCF2H
+
Rose Bengal (0.48 mmol)
White LED (5 W)
DMSO (24 mL)
R.T.
Ph
2j
6 mmol, 1.02 g
3j
1.09 g, 64%
9 mmol
7
8
9
SCHEME 7. Scale-up of the difluoromethylselenolation reaction
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In summary, we report the synthesis of a novel shelf-stable reagent TsSeCF2H, which
allows direct difluoromethylselen-olations of aryl amines via in situ generated
aryldiazonium salts under visible-light catalysis for the first time. Mechanistic
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investigations performed using F NMR spectroscopy, and radical trapping experiments
confirmed the intermediacy of free radicals in this reaction. The readily accessible
reagents, metal-free reaction conditions, and the broad substrate scope provide a green
and efficient protocol for preparation of aryl difluoromethylselenylether. Exploration of
TsSeCF2H-mediated difluoromethylselenolation applications of other relevant organic
molecules is currently underway in our laboratory.
EXPERIMENTAL SECTION
1) General Experimental Methods.
All solvents were distilled prior to use. For chromatography, 200-300 mesh silica gel
(Qingdao, China) was employed. The light-promoted reactions were done using standard
LED lamp with five light emitting diodes (12-28 V, 5W, 465-470 nm). The distance from
the light source to the irradiation vessel is 3 cm. 1H, 13C NMR and 19F NMR spectra were
recorded at 400 MHz and 100 MHz with Brucker ARX 400 spectrometer. Chemical
shifts are reported in ppm using tetramethylsilane(TMS) as internal standard. The
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GC-MS spectra were recorded on Thermo Scientific Trace 1300. High resolution mass
spectra were obtained on a Bruker SCION 436-GC SQ mass spectrometer or on a Bruker
Apex IV FTMS spectrometer. Melting points are reported as uncorrected. Except
BnSeCF2H8a, 1aa18 and 1ad19 were prepared according to the literature procedures, All
reagents were obtained from commercial suppliers and used without further purification.
2) Preparation of 1
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Under an argon atmosphere, to a flask equipped with a magnetic stir bar was added the
benzyl (difluoromethyl)selane (10 mmol , 1.0 equiv.), sulfuryl chloride (10 mmol , 1.0
equiv.) and anhydrous DCM (4 mL). The mixture was stirred at 0 oC for 3 hours and then
transferred to another flask with a solution of TsNa (11 mmol. 1.1 equiv.) in anhydrous
o
DCM (16 mL) which had been cooled down to -78 C. The mixture was stirred about
o
10-15 minutes at -78 C and then filtered over a pad of silica. The filtrate was
concentrated to dryness and purified directly by silica gel chromatography, eluting with
1
petroleum ether/DCM (20:1), to give compound 1 (yellow liquid, 2.0 g, 70% yield). H
NMR (400 MHz, CDCl3) δ 7.78 (d, J = 8.0 Hz, 2H), 7.63 (t, J = 54.4 Hz, 1H), 7.37 (d, J
= 8.0 Hz, 2H), 2.47 (s, 3H); 19F{1H} NMR (376 MHz, CDCl3) δ -90.55 (s, 2F); 13C{1H}
NMR (100 MHz, CDCl3) δ 145.9, 145.3, 130.2, 126.7, 120.7 (t, J = 290.1 Hz), 21.9; IR
(KBr): 2958, 2916, 2848, 1593, 1490, 1401, 1331, 1290, 1305, 1259, 1173, 1135, 1058,
1015, 809, 700, 682 cm-1; HRMS (ESI-quadrupole) m/z:
C8H9F2O2SSe 286.9451; Found 286.9524.
[M+H]+ Calcd for
3) General procedure for the dimethylselenolation of aryl amines
To a sealed tube was added amine (0.25 mmol, 1.0 equiv.), p-TsOH (0.30 mmol, 1.2
equiv.) and Rose Bengale (0.02 mmol, 0.08 equiv.) and dry DMSO (1.0 mL). The
reaction mixture was stirred for 5 minutes, then t-BuONO (0.30 mmol, 1.2 equiv.) and
Se-(difluoromethyl) 4-methylbenzenesulfonoselenoate (1, 0.375 mmol 1.5 equiv.) was
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added in turn, and the mixture was irradiated with white light LED (5 W) at room
temperature for 10 h. After the irradiation, water (5 mL) was added to give an emusion
which was extracted with ethyl acetate (3 × 5mL). The combined organic phase was
washed with brine and dried over by anhydrous Na2SO4. The solvent was removed in
vacuo, and the residue which was purified by silica gel chromatography, eluting with
petroleum ether/ethyl acetate (from 60:1 to 2:1), to give compound 3.
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4) Characteristic data for 3a-3w and 3aa-3ad
ethyl 4-((difluoromethyl)selanyl)benzoate (3a): Yellow oil (56 mg, 80% yield from
general procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for column
chromatography, 1H NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.4 Hz, 2H), 7.71 (d, J = 8.0
Hz, 2H), 7.22 (t, J = 54.8 Hz, 1H), 4.39 (q, J = 7.2 Hz, 2H), 1.39 (t, J = 7.2 Hz, 3H);
13
19F{1H} NMR (376 MHz, CDCl3) δ -89.93 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ
165.9, 135.4, 131.3, 130.4, 129.4, 116.7 (t, J = 290.0 Hz), 61.3, 14.3; IR (KBr):2982,
1712, 1592, 1465, 1395, 1367, 1267, 1178, 1105, 1073, 1043, 1013, 850, 748, 757, 693,
683, 664 cm-1; HRMS (EI-quadrupole) m/z: Calcd for [M]+ C10H10O2F2Se 279.9814;
Found 279.9807.
((difluoromethyl)selanyl)benzoic acid (3b): White solid (42 mg, 67% yield from general
procedure), petroleum ether/ethyl acetate 5:1 (v/v) as eluents for column chromatography.
1H NMR (400 MHz, DMSO - d6) δ 8.00 (d, J = 8.4 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H),
7.50 (t, J = 54.8 Hz, 1H); 19F{1H} NMR (376 MHz, DMSO-d6) δ -92.40 (s, 2F); 13C{1H}
NMR (100 MHz, DMSO-d6) δ 167.6, 135.0, 131.2, 130.1, 129.7, 117.2 (t, J = 285.0 Hz).
IR (KBr): 3472, 3090, 3047,2920, 2850, 2727, 2667, 2551, 1666, 1599, 1587, 1563, 1425,
1397, 1370, 1313, 1289, 1277,1245, 1181, 1128, 1075, 1060, 1036, 1015, 961, 866, 785,
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695, 670, 543 cm-1; m.p.190-191 C; HRMS (ESI-quadrupole) m/z: Calcd for [M-H]-
5
6
C8H5O2F2Se 250.9429; Found 250.9425.
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(difluoromethyl)(4-nitrophenyl)selane (3c)7f: White solid (26 mg, 41% yield from
general procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for column
chromatography, 1H NMR (400MHz, CDCl3）δ 8.19 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 8.4
Hz, 2H), 7.27 (t, J = 54.4 Hz, 1H); 19F{1H} NMR (376MHz, CDCl3) δ -89.9 (s, 2F);
13C{1H} NMR (100 MHz, CDCl3) δ 148.5, 136.1, 132.4, 124.3, 116.2 (t, J = 288.0 Hz).
The spectral data are in accordance with the literature report.
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((difluoromethyl)selanyl)benzonitrile (3d)7f: White solid (31 mg, 53% yield from general
procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for column
chromatography, 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 8.4
19
Hz, 2H), 7.23 (t, J = 55.6 Hz, 1H); F{1H} NMR (376 MHz, CDCl3) δ -89.87 (s, 2F).
13C{1H} NMR (100 MHz, CDCl3) δ 136.0, 132.7, 130.0, 118.0, 116.2 (t, J = 289.0 Hz),
113.2. The spectral data are in accordance with the literature report.
4-((difluoromethyl)selanyl)benzamide (3e): White solid (45.7 mg, 73% yield from
general procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for column
chromatography, 1H NMR (400 MHz, Methanol-d4) δ 7.86 (d, J = 8.4 Hz, 2H), 7.75 (d, J
= 8.4 Hz, 2H), 7.49 (t, J = 54.8 Hz, 1H); 19F{1H} NMR (376 MHz, Methanol-d4) δ
-92.58 (s, 2F). 13C{1H} NMR (100 MHz, Methanol-d4) δ 170.0, 135.3, 134.4, 128.2,
127.2, 117.2 (t, J = 289.0 Hz); IR (KBr): 3435, 2957, 2927, 2870, 1716, 1592, 1456,
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1395, 1370, 1287, 1178, 1116, 1077, 1062, 1015, 759, 685 cm-1; m.p. 149-151oC; HRMS
(ESI-quadrupole) m/z: Calcd for [M+Na]+ C8H7NOF2SeNa 273.9553; Found 273.9540.
(difluoromethyl)(4-methoxyphenyl)selane (3f)7f: Light yellow oil (42 mg, 70% yield
from general procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for column
chromatography, 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 8.4 Hz, 2H), 7.09 (t, J = 55.2
Hz, 1H), 6.89 (d, J = 8.8 Hz, 2H), 3.82 (s, 3H); 19F{1H} NMR (376 MHz, CDCl3) δ
-91.08 (s, 2F). 13C{1H} NMR (100 MHz, CDCl3) δ 161.0, 138.6, 117.2 (t, J = 288.0 Hz),
115.3, 113.6, 55.5. The spectral data are in accordance with the literature report.
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((difluoromethyl)selanyl)phenol (3g) 7f: Light yellow oil (41 mg, 61% yield from general
procedure), petroleum ether/ethyl acetate 40:1 (v/v) as eluents for column
chromatography. 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 8.8 Hz, 2H), 7.09 (t, J =55.6
Hz, 1H), 6.82 (d, J = 8.8 Hz, 2H), 5.04 (s, 1H); 19F{1H} NMR (376MHz, CDCl3) δ
-91.06 (s, 2F). 13C{1H} NMR (100 MHz, CDCl3) δ 157.1, 138.8, 117.1 (t, J = 288.0 Hz),
116.8, 113.9. The spectral data are in accordance with the literature report.
[1,1'-biphenyl]-4-yl(difluoromethyl)selane (3h) 7f: White solid (49 mg, 69.2% yield from
general procedure), petroleum ether/ethyl acetate 60:1(v/v) as eluents for column
1
chromatography, H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 4.8 Hz, 2H), 7.60-7.58 (m,
4H), 7.47 (t, J = 7.2 Hz, 2H), 7.39 (t, J = 7.6 Hz, 1H), 7.21 (t, J = 55.6 Hz, 1H);19F{1H}
13
NMR (376 MHz, CDCl3) δ -90.21 (s, 2F). C{1H} NMR (100 MHz, CDCl3) δ 142.6,
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140.1, 136.9, 129.1, 128.3, 128.1, 127.3, 122.4, 117.2 (t, J = 287.0 Hz). The spectral data
are in accordance with the literature report.
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(difluoromethyl)(2-methoxyphenyl)selane (3i): Colorless oil (48 mg, 80% yield from
general procedure), petroleum ether/ethyl acetate 20:1 (v/v) as eluents for column
chromatography. 1H NMR (400 MHz, CDCl3) δ 7.58 (d, J = 7.2Hz, 1H), 7.37 (td, J = 7.8
Hz, 1.2 Hz, 1H), 7.30 (t, J = 56.0 Hz, 1H), 6.97-6.93 (m, 2H), 3.90 (s, 3H); 19F{1H}
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NMR (376 MHz, CDCl3) δ -91.41 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ 158.7,
136.1, 130.8, 121.7, 116.7 (t, J = 286.0 Hz), 113.8, 111.2, 56.0; IR (KBr): 2939, 1581,
1477, 1434, 1273, 1247, 1181, 1164, 1125, 1055, 1032, 752, 693cm-1; HRMS
(EI-quadrupole) m/z: Calcd for [M]+ C8H8OF2Se 237.9708; found 237.9702.
[1,1'-biphenyl]-2-yl(difluoromethyl)selane (3j): Light yellow oil (54 mg, 76% yield from
general procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for column
1
chromatography. H NMR (400MHz, CDCl3）δ 7.76 (d, J = 7.6 Hz, 1H), 7.46-7.39 (m,
19
5H), 7.37-7.30 (m, 3H), 7.01 (t, J = 55.2 Hz, 1H); F{1H} NMR (376MHz, CDCl3) δ
-90.6 (s, 2F); 13C{1H} NMR (100 MHz, CDCl3) δ 146.4, 141.7, 135.4, 130.8, 129.4,
129.1, 128.5, 128.2, 127.9, 124.9, 117.5 (t, J = 287.0 Hz); IR (KBr): 3054, 1582, 1496,
1462, 1446, 1424, 1291, 1270, 1026, 1006, 915, 871, 771, 746, 698cm-1; HRMS
(EI-quadrupole) m/z: Calcd for [M]+ C13H10F2Se 283.9916; Found 283.9910.
(3-((difluoromethyl)selanyl)phenyl)(phenyl)methanone (3k): Colorless oil (56 mg, 72%
yield from general procedure), petroleum ether/ethyl acetate 60:1(v/v) as eluents for
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column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.10 (s, 1H), 7.89 (d, J = 8.0Hz,
1H), 7.86-7.84 (m, 1H), 7.81-7.79 (m, 2H), 7.64-7.60 (m, 1H), 7.53-7.48 (m, 3H), 7.22 (t,
J = 55.2 Hz, 1H). 19F{1H} NMR (376 MHz, CDCl3) δ -90.28 (s, 2F); 13C{1H} NMR (100
MHz, CDCl3) δ 195.6, 140.1, 138.9, 137.7, 137.1, 133.0, 131.0, 130.2, 129.5, 128.6,
123.8, 116.6 (t, J = 289.0 Hz); IR (KBr): 3059, 1656, 1597, 1580, 1565, 1447, 1400,
1309, 1267, 1180, 1152, 1040, 998, 945, 926, 849, 813, 782, 748, 713, 685, 664 cm-1;
HRMS (ESI-quadrupole) m/z: Calcd for [M+H]+ C14H11OF2Se 312.9938; found
312.9950.
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(difluoromethyl)(mesityl)selane (3l): Light yellow oil (49 mg, 79% yield from general
procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for column
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chromatography. H NMR (400 MHz, CDCl3) δ 7.00 (s, 2H), 6.98 (t, J = 55.2 Hz, 1H),
19
13
2.54 (s, 6H), 2.29 (s, 3H); F{1H} NMR (376 MHz, CDCl3) δ -89.34 (s, 2F). C{1H}
NMR (100 MHz, CDCl3) δ 144.5, 140.3, 129.1, 122.4, 117.6 (t, J = 288.0 Hz), 25.0, 21.2;
IR (KBr): 2924, 1598, 1457, 1377, 1280, 1269, 1059, 1005, 1020, 849, 730, 713, 713,
687, 660cm-1; HRMS (EI-quadrupole) m/z: Calcd for [M]+ C10H12F2Se 250.0072; Found
250.0068.
(2,6-diethylphenyl)(difluoromethyl)selane (3m): Light yellow oil (30 mg, 46% yield
from general procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for column
1
chromatography. H NMR (400 MHz, CDCl3) δ 7.32 (t, J = 7.2 Hz, 1H), 7.19 (d, J =
7.6Hz, 2H), 6.98 (t, J = 55.2 Hz, 1H), 3.00 (q, J = 7.2 Hz, 4H), 1.23 (t, J = 7.6 Hz, 6H);
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19F{1H} NMR (376 MHz, CDCl3) δ -89.20 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ
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150.5, 130.7, 126.9, 124.7, 118.0 (t, J = 288.0 Hz), 30.9, 16.0; IR (KBr): 3440, 2954,
2918, 2849, 1630, 1462 cm-1; HRMS (EI-quadrupole) m/z: Calcd for [M]+ C11H14F2Se
264.0229; Found 264.0222.
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5-((difluoromethyl)selanyl)-1,3-dihydro-2H-benzo[d]imidazol-2-one (3n): White solid
(38 mg, 57% yield from general procedure), petroleum dichloromethane/methanol
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20:1(v/v) as eluents for column chromatography, H NMR (400 MHz, Methanol-d4) δ
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7.37-7.35 (m, 2H), 7.32 (t, J = 55.2 Hz, 1H), 7.05 (d, J = 8.8 Hz, 1H); F{1H} NMR
(376 MHz, Methanol-d4) δ -93.23 (s, 2F); 13C{1H} NMR(100 MHz, Methanol-d4) δ
156.4, 130.8, 130.3, 130.0, 117.5 (t, J = 286.0 Hz), 117.1, 114.2, 109.6; IR (KBr): 3176,
3107, 3087, 3013, 2883, 2829, 2787, 2727, 1716, 1626, 1483, 1366, 1291, 1271, 1197,
1064, 1047, 1025, 883, 804, 783, 749, 707, 695, 675, 598cm-1; m.p. 279-281oC; HRMS
(ESI-quadrupole) m/z: Calcd for [M +H]+ C8H7F2N2OSe 264.9686; Found 264.9691.
5-((difluoromethyl)selanyl)benzo[d][1,3]dioxole (3o)7f: Light yellow oil (30 mg, 48%
yield from general procedure), petroleum ether/ethyl acetate 50:1 (v/v) as eluents for
column chromatography. 1H NMR (400 MHz, CDCl3) δ 7.17 (dd, J = 7.6 Hz, 1.2 Hz, 1H),
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7.13 (s, 1H), 7.10 (t, J = 55.6 Hz, 1H), 6.79 (d, J = 8.0 Hz 1H), 6.0 (s, 2H); F{1H}
13
NMR (376 MHz, CDCl3) δ -91.04 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ 149.4,
148.4, 131.4, 117.1 (t, J = 287.0 Hz), 116.9, 114.4 (t, J = 3.0 Hz), 114.3, 101.7. The
spectral data are in accordance with the literature report.
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5-((difluoromethyl)selanyl)isoindoline-1,3-dione (3p): White solid (41 mg, 59% yield
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from general procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for column
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chromatography. H NMR (400 MHz, CDCl3) δ 8.36 (s, 1H), 8.15 (s, 1H), 8.05 (dd, J =
9
7.6 Hz, 0.8 Hz, 1H), 7.86 (d, J = 8.0Hz, 1H), 7.29 (t, J = 54.8 Hz, 1H); 19F{1H}
NMR(376 MHz, CDCl3) δ -89.83 (s, 2F); 13C{1H} NMR (100 MHz, CDCl3) δ 167.4,
167.2, 141.3, 133.5, 133.1, 131.7, 130.5, 124.5, 116.1 (t, J = 289.0 Hz); IR (KBr): 3854,
3736, 3676, 3650, 3629, 3467, 3191, 3078, 2714, 1770, 1746, 1717, 1604, 1421, 1370,
1353, 1293, 1190, 1111, 1054, 1040, 859, 752, 739, 692, 674, 650, 642, 587, 556,
500cm-1; m.p. 141-142oC; HRMS (ESI-quadrupole) m/z: Calcd for [M]+ C9H5NO2F2Se
276.9454; Found 276.9432.
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6-((difluoromethyl)selanyl)isobenzofuran-1(3H)-one (3q): White solid (32 mg, 47%
yield from general procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for
column chromatography, 1H NMR (400 MHz, CDCl3) δ 8.21 (s, 1H), 7.97 (d, J = 8.0 Hz,
1H), 7.52 (d, J = 8.0 Hz, 1H), 7.21 (t, J = 54.8 Hz, 1H), 5.35 (s, 2H); 19F{1H} NMR (376
13
MHz, CDCl3) δ -90.3 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ 169.9, 147.7, 141.8,
133.8, 127.3, 124.5, 123.4, 116.2 (t, J = 288.0 Hz), 69.7; IR (KBr): 3497, 3065, 3023,
2977, 2952, 2878, 1751, 1715, 1660, 1609, 1448, 1411, 1358, 1291, 1262, 1210, 1194,
1125, 1106, 1051, 1034, 1025, 1005, 912, 862, 831, 770, 692, 666, 627, 509 cm-1; m.p.
109-110oC; HRMS (ESI-quadrupole) m/z: Calcd for [M+Na]+ C9H6O2F2SeNa 286.9393;
Found 286.9383.
7-((difluoromethyl)selanyl)-4-methyl-2H-chromen-2-one (3r): White solid (33 mg, 46%
1
yield), petroleum ether/ethyl acetate 5:1(v/v) as eluents for column chromatography, H
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NMR (400 MHz, CDCl3) δ .7.60 (d, J = 7.2 Hz, 1H), 7.56-7.35 (m, 2H), 7.24 (t, J = 54.8
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Hz, 1H), 6.33 (s, 1H), 2.44 (s, 3H); C{1H} NMR (100 MHz, CDCl3) δ 160.0, 153.4,
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151.8, 131.2, 127.7 (t, J = 3.0 Hz), 125.3, 123.9, 120.7, 116.5 (t, J = 289.0 Hz), 116.2,
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18.7; F{1H} NMR (376 MHz, CDCl3) δ -89.98 (s, 2F); IR (KBr): 3427, 3085, 3060,
2962, 2926, 1766, 1728, 1716, 1682, 1622, 1594, 1542, 1434, 1389, 1289, 1247, 1174,
1090, 1051, 1039, 1008, 946, 904, 868, 822, 708, 675, 563cm-1; m.p. 150-152oC; HRMS
(ESI-quadrupole) m/z: Calcd for [M+Na]+ C11H8O2F2SeNa 312.9550; Found 312.9534.
2-((difluoromethyl)selanyl)anthracene-9,10-dione (3s): Light yellow solid (56 mg, 59%
yield from general procedure), petroleum ether/ethyl acetate 50:1(v/v) as eluents for
1
column chromatography. H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 1.2 Hz, 1H),
8.32-8.30 (m, 2H), 8.26 (d, J = 8.4 Hz, 1H), 8.04 (dd, J = 8 Hz, 1.6 Hz, 1H), 7.84-7.81 (m,
2H), 7.33 (t, J = 54.8 Hz, 1H); 19F{1H} NMR (376 MHz, CDCl3) δ -89.72 (s, 2F); 13C{1H}
NMR (100 MHz, CDCl3) δ 182.9, 182.7, 140.7, 134.9, 134.8, 134.2, 133.9, 133.8, 133.7,
133.6, 132.4, 128.6, 127.9, 127.8, 116.7 (t, J = 288.0 Hz); IR (KBr): 3455, 3070, 3031,
2963, 2923, 2852, 1676, 1580, 1322, 1283, 1259, 1170, 1054, 1043, 953, 927, 853, 797,
710, 675, 632cm-1; m.p. 128-130oC; HRMS (EI-quadrupole) m/z: Calcd for [M]+
C15H8O2F2Se 337.9658; Found 337.9651.
1-((difluoromethyl)selanyl)anthracene-9,10-dione (3t): Light yellow solid (51 mg, 61%
yield from general procedure), petroleum ether/ethyl acetate 30:1(v/v) as eluents for
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column chromatography. H NMR (400 MHz, CDCl3) δ 8.31-8.24 (m, 3H), 7.94 (d, J =
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NMR (376 MHz, CDCl3) δ -97.99 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ 184.1,
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182.5, 136.1, 135.8, 134.6, 134.5, 134.0, 133.8, 133.2, 132.7, 130.5, 127.6, 127.3, 125.9,
117.1(t, J = 285.0 Hz); IR (KBr): 3439, 3076, 2973, 1978, 1854, 1665, 1642, 1593, 1568,
1447, 1419, 1338, 1313, 1277, 1242, 1179, 1164, 1125, 1097, 1064, 1032, 951, 926, 881,
805, 727, 706, 682, 642, 620cm-1; m.p. 189-190oC; HRMS (ESI-quadrupole) m/z: Calcd
for [M+H]+ C15H9O2F2Se 338.9730; Found 338.9698.
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3-((difluoromethyl)selanyl)quinoline (3u): Light yellow solid (40 mg, 60% yield from
general procedure), petroleum ether/ethyl acetate 50:1(v/v) as eluents for column
chromatography. 1H NMR (400 MHz, CDCl3) δ 9.07 (d, J = 1.6 Hz, 1H), 8.53 (d, J = 0.8
Hz, 1H), 8.13 (d, J = 8.8 Hz, 1H), 7.83-7.82 (m, 2H), 7.61 (t, J = 7.2Hz, 1H), 7.23 (t, J =
54.8Hz, 1H); 19F{1H} NMR (376 MHz, CDCl3) δ -89.98 (s, 2F); 13C{1H} NMR (100
MHz, CDCl3) δ 155.3, 147.9, 144.5, 131.0, 129.6, 128.5, 127.9, 127.6, 117.2, 116.1 (t, J
= 289.0Hz); IR (KBr): 3448, 3048, 2964, 1853, 1615, 1581, 1563, 1491, 1368, 1353,
1318, 1291, 1254, 1058, 1041, 1017, 952, 910, 780, 750, 688, 629, 174cm-1; m.p.
76-77oC; HRMS (ESI-quadrupole) m/z: Calcd for [M+H]+ C10H8NF2Se 259.9785; Found
259.9766.
6-((difluoromethyl)selanyl)benzo[d]thiazole (3v): Colorless oil (30 mg, 49% yield from
general procedure), petroleum ether/ethyl acetate 60:1(v/v) as eluents for column
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chromatography. H NMR (400 MHz, CDCl3) δ 9.06 (s, 1H), 8.31 (d, J = 1.2 Hz, 1H),
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19F{1H} NMR (376 MHz, CDCl3) δ -90.34 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ
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155.7, 154.0, 135.0, 134.4, 130.3, 124.5, 120.3, 116.9 (t, J = 288.0 Hz); IR (KBr): 3059,
1582, 1538, 1456, 1429, 1389, 1290, 1268, 1200, 1157, 1135, 1035, 877, 839, 805, 742,
691, 670 cm-1; HRMS (ESI-quadrupole) m/z: Calcd for [M+H]+ C8H6NF2SSe 265.9349;
Found 265.9335.
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ethyl 5-((difluoromethyl)selanyl)benzofuran-2-carboxylate (3w): White solid (41 mg,
51% yield from general procedure), petroleum ether/ethyl acetate 20:1(v/v) as eluents for
column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 1.2 Hz, 1H), 7.74
(dd, J = 8.8 Hz, 1.6 Hz 1H), 7.58 (d, J = 8.4 Hz, 1H), 7.52 (s, 1H), 7.18 (t, J = 55.2 Hz,
1H). 4.46 (q, J = 7.2 Hz, 2H) 1.44 (t, J = 7.2Hz, 3H); 19F{1H} NMR (376 MHz, CDCl3) δ
-90.74 (s, 2F); 13C{1H} NMR (100 MHz, CDCl3) δ 159.3, 156.1, 146.9, 135.8, 131.8,
128.5, 117.9, 116.9 (t, J = 288.0 Hz), 113.6, 113.3, 61.9, 14.4; IR (KBr): 3059, 1582,
1538, 1456, 1429, 1389, 1290, 1268, 1200, 1157, 1135, 1035, 877, 839, 805, 742, 691,
670cm-1; m.p. 105-106oC; HRMS (ESI-quadrupole) m/z: Calcd for [M+Na]+
C12H10O3F2SeNa 342.9655; Found 342.9640.
ethyl 2-(4-((difluoromethyl)selanyl)phenoxy)-2-methylpropanoate (3aa): Colorless oil
(65 mg, 77% yield from general procedure), petroleum ether/ethyl acetate 50:1(v/v) as
1
eluents for column chromatography. H NMR (400 MHz, CDCl3) δ 7.53 (d, J = 8.8 Hz,
2H), 7.09 (t, J = 55.6 Hz, 1H), 6.79 (dd, J = 11.6 Hz, 2.8 Hz, 2H), 4.23 (q, J = 7.2 Hz,
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2H), 1.62 (s, 6H), 1.23 (t, J = 7.2Hz, 3H); 19F{1H} NMR (376 MHz, CDCl3) δ -90.87 (s,
2F); 13C{1H} NMR (100 MHz, CDCl3) δ 174.0, 157.1, 138.0, 129.3, 119.5, 117.0 (t, J =
288.0 Hz), 79.4, 61.7, 25.5, 14.2; IR (KBr): 2990, 1731, 1585, 1570, 1488, 1467, 1383,
1365, 1281, 1239, 1176, 1136, 1058, 968, 915, 827, 765, 712, 691, 670cm-1; HRMS
(ESI-quadrupole) m/z: Calcd for [M+Na]+ C13H16O3F2SeNa 361.0125; Found 361.0113 .
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4-((difluoromethyl)selanyl)-2-(2,6-dioxopiperidin-3-yl)isoindoline-1,3-dione
(3ab):
White solid (42 mg, 44% yield from general procedure), petroleum ether/ethyl acetate
1
1:1(v/v) as eluents for column chromatography. H NMR (400 MHz, CDCl3) δ 7.99 (s,
1H), 7.91 (d, J = 7.6 Hz, 1H), 7.83 (d, J = 7.2 Hz, 1H), 7.70 (t, J = 8.0 Hz, 1H), 7.48 (t, J
= 54.4 Hz, 1H), 4.99 (dd, J = 12.0 Hz, 5.4 Hz, 2H), 2.95-2.71 (m, 3H), 2.20-2.14 (m, 1H);
13
19F{1H} NMR (376 MHz, CDCl3) δ -91.82 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ
170.6, 167.7, 166.9, 166.4, 137.3, 135.1, 133.4, 130.4, 126.5, 123.1, 116.0 (t, J = 288.0
Hz), 49.7, 31.5, 22.7; IR (KBr): 3208, 3094, 1786, 1771, 1712, 1391, 1368, 1342, 1325,
1308, 1261, 1197, 1117, 1048, 1016, 993, 891, 813, 801, 736, 720, 663, 613, 572, 533,
470cm-1; m.p. 236-238oC; HRMS (ESI-quadrupole) m/z: Calcd for [M+Na]+
C14H10N2O4F2SeNa 410.9666; Found 410.9667.
4-((difluoromethyl)selanyl)-N-(5-methylisoxazol-3-yl)benzenesulfonamide (3ac): White
solid (44 mg, 48% yield from general procedure), petroleum ether/ethyl acetate 2:1(v/v)
as eluents for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 7.81
(d, J = 8.8 Hz, 2H), 7.75 (d, J = 8.8 Hz, 2H), 7.22 (t, J = 54.8 Hz, 1H), 6.25 (s, 1H), 2.39
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(s, 3H); F{1H} NMR (376 MHz, CDCl3) δ -89.69 (s, 2F); C{1H} NMR (100 MHz,
CDCl3) δ 171.5, 157.6, 140.0, 136.1, 130.1, 127.9, 116.5 (t, J = 289.0 Hz), 95.7, 12.9; IR
(KBr): 3092, 2993, 2915, 2850, 2811, 1617, 1474, 1408, 1387, 1351, 1295, 1265, 1184,
1173, 1072, 1058, 1043, 1011, 938, 915, 826, 802, 750, 665, 601, 563cm-1; m.p.
161-162oC; HRMS (ESI-quadrupole) m/z: Calcd for [M+Na]+ C11H10N2O3F2SSeNa
390.9438; Found 390.9423.
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(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 4-((difluoromethyl)selanyl)benzoate (3ad):
Colorless oil (78 mg, 80% yield from general procedure), petroleum ether/ethyl acetate
50:1(v/v) as eluents for column chromatography. 1H NMR (400 MHz, CDCl3) δ 8.01 (d,
J = 8.4 Hz, 2H), 7.72 (d, J = 8.0 Hz, 2H), 7.21 (t, J = 54.8 Hz, 1H), 6.79 (td, J = 11.2 Hz,
4.0 Hz, 1H), 4.23 (q, J = 7.2 Hz, 2H). 1.62 (s, 6H) 1.23 (t, J = 7.2Hz, 3H); 19F{1H} NMR
(376 MHz, CDCl3) δ -89.91 (s, 2F); C{1H} NMR (100 MHz, CDCl3) δ 165.5, 135.6,
13
131.7, 130.5, 129.4 (t, J = 3.0 Hz), 116.8 (t, J = 287.0 Hz), 75.4, 47.4, 41.0, 35.4, 31.6,
26.6, 23.7, 22.2, 20.9, 16.6; IR (KBr): 3436, 2957, 2925, 2870, 1716, 1592, 1456, 1392,
1370, 1287, 1270, 1178, 1116, 1077, 1063, 1015, 961, 759, 685cm-1; HRMS
(ESI-quadrupole) m/z: Calcd for [M+Na]+ C18H24O2F2SeNa 413.0802; Found 413.0809 .
AUTHOR INFORMATION
Corresponding Author
*E-mail: lukui@tust.edu.cn; hxxyzhx@mail.tjnu.edu.cn;
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Notes
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The authors declare no competing financial interest.
ASSOCIATED CONTENT
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Supporting Information
Mechanistic studies for reagent 1 under white LED, by 19F NMR monitoring, and by
trapping experiments as well as Spectroscopic for compounds 1, 3a-3w and 3aa-3ad is
available free of charge via the Internet at http://pubs.acs.org.
ACKNOWLEDGMENTS
The authors sincerely thank the financial support from National Science Foundation of
China (Grants 21572158) and Tianjin Natural Science Foundation (Grants
18JCQNJC76600).
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9 For Selected examples see: (a) Mo, F.; Jiang, Y.; Qiu, D.; Zhang, Y.; Wang, J. Direct
Conversion of Arylamines to Pinacol Boronates: A Metal-Free Borylation Process.
Angew. Chem. Int. Ed. 2010, 49, 1846−1849. (b) Yu, J.; Zhang, L.; Yan, G. Metal‐Free,
Visible Light-Induced Borylation of Aryldiazonium Salts: A Simple and Green Synthetic
Route to Arylboronates. Adv. Synth. Catal. 2012, 354, 2625−2628. (c) Qiu, D.; Jin, L.;
Zheng, Z.; Meng, H.; Mo, F.; Wang, X.; Zhang, Y.; Wang, J. Synthesis of Pinacol
Arylboronates from Aromatic Amines: A Metal-Free Transformation. J. Org. Chem.
2013, 78, 1923−1933. (d) Qiu, D.; Zhang, Y.; Wang, J. Direct Synthesis of Arylboronic
Pinacol Esters from Arylamines. Org. Chem. Front. 2014, 1, 422−425. (e) Qiu, D.; Meng,
H.; Jin, L.; Tang, S.; Wang, S.; Mo, F.; Zhang, Y.; Wang, J. Synthesis of Arylboronic
Pinacol Esters from Corresponding Arylamines. Org. Synth. 2014, 91, 106−115. (f) Xu,
Y.-L.; Yang, X.-Y.; Fang, H. Additive- and Photocatalyst-Free Borylation of Arylazo
Sulfones under Visible Light. J. Org. Chem. 2018, 83, 12831−12837.
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Carbon–Phosphorus Bond Formation via a Sandmeyer-Type Reaction. J. Org. Chem.
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11 For Selected examples see: (a) Adams, D. J.; Goddard, A.; Clark, J. H.; Macquarrie, D.
J. Trifluoromethylthiodediazoniation: A Simple, Efficient Route to Trifluoromethyl Aryl
Sulfides. Chem. Commun. 2000, 987−988. (b) Majek, M.; Jacobivon Wangelin, A.
Organocatalytic Visible Light Mediated Synthesis of Aryl Sulfides. Chem. Commun.
2013, 48, 5507−5509. (c) Koziakov, D.; Majek, M.; Jacobivon Wangelin, A. Metal-Free
Radical Thiolations Mediated by Very Weak Bases. Org. Biomol. Chem. 2016, 14,
11347−11352. (d) Matheis, C.; Wagner, V.; Goossen, L. J. Sandmeyer-Type
Trifluoromethylthiolation and Trifluoromethylselenolation of (Hetero) Aromatic Amines
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Catalyzed by Copper. Chem. - Eur. J. 2016, 22, 79−82. (e) Koziakov, D.; Majek, M.;
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12 For Selected examples see: (a) Qiu, D.; Meng, H.; Jin, L.; Wang, S.; Tang, S.; Wang,
X.; Mo, F.; Zhang, Y.; Wang, J. Synthesis of Aryl Trimethylstannanes from Aryl Amines:
A Sandmeyer-Type Stannylation Reaction. Angew. Chem. Int. Ed. 2013, 52,
11581−11584. (b) Qiu, D.; Wang, S.; Tang, S.; Meng, H.; Jin, L.; Mo, F.; Zhang, Y.;
Wang, J. Synthesis of Trimethylstannyl Arylboronate Compounds by Sandmeyer-Type
Transformations and Their Applications in Chemoselective Cross-Coupling Reactions. J.
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13 For Selected examples see: (a) Wang, X.; Xu, Y.; Mo, F.; Ji, G.; Qiu, D.; Feng, J.; Ye,
Y.; Zhang, S.; Zhang, Y.; Wang, J. Silver-Mediated Trifluoromethylation of
Aryldiazonium Salts: Conversion of Amino Group into Trifluoromethyl Group. J. Am.
Chem. Soc. 2013, 135, 10330−10333. (b) Dai, J.-J.; Fang, C.; Xiao, B.; Yi, J.; Liu, Z.-J.;
Lu, X.; Liu, L.; Fu, Y. Copper-Promoted Sandmeyer Trifluoromethylation Reaction J.
Am. Chem. Soc. 2013, 135, 8436−8439. (c) Danoun, G.; Bayarmagnai, B.; Grünberg, M.
F.; Goossen, L. J. Sandmeyer Trifluoromethylation of Arenediazonium
Tetrafluoroborates. Angew. Chem. Int. Ed. 2013, 52, 7972−7975. (d) Wang, X.; Xu, Y.;
Zhou, Y.; Zhang, Y.; Wang, J. Conversion of Aromatic Amino into Trifluoromethyl
Groups through a Sandmeyer-Type Transformation. Synthesis. 2014, 46, 2143−2148. (e)
Bayarmagnai, B.; Matheis, C.; Risto, E.; Goossen, L. J. One-Pot Sandmeyer
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2343−2348.
14 Zhao, X.; Zheng, X.-C.; Tian, M.-M.; Tong, Y.-F.; Yang, B.; Wei, X.-F.; Qiu, D.; Lu,
K. Visible-Light Photocatalytic Trifluoromethylthiolation of Aryldiazonium Salts:
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