Borylation of Diazonium Salts by Highly Emissive and Crystalline Carbon Dots in Water

Article abstract of DOI:10.1002/cssc.202000277

Efficient borylation reaction of diazonium salts in water is realized for the first time by using easily prepared, highly emissive and crystalline carbon dots. Electron-donating and electron-withdrawing groups on diazonium salts were well tolerated with moderate to good conversion efficiency. Compared with widely used metal complexes, organic dyes and quantum dots, the approach presented herein uses carbon dots, which are nontoxic and possess good biological and medicinal compatibility and high reactivity. Therefore, this approach presents a new prospective use for carbon dots in green chemistry.

Full text of DOI:10.1002/cssc.202000277

Accepted Article
Title: Borylation of Diazonium Salts by Highly Emissive and Crystalline
Carbon Dots in Water
Authors: Li-Zhu Wu, Tao Lei, Si-Meng Wei, Ke Feng, Bin Chen, and
Chen-Ho Tung
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.202000277
Link to VoR: http://dx.doi.org/10.1002/cssc.202000277
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ChemSusChem
10.1002/cssc.202000277
Supporting Information
Borylation of Diazonium Salts by Highly Emissive and Crystalline
Carbon Dots in Water
[
a, b]
[a, b]
[a, b]
[a, b]
[a, b]
Tao Lei,
Si-Meng Wei,
Ke Feng,
Bin Chen,
Chen-Ho Tung,
and
[
a, b]
Li-Zhu Wu,*
*
Email of corresponding author: lzwu@mail.ipc.ac.cn
Table of Contents
1
2
3
4
5
6
. Materials and Methods.............................................................................................S2
. Preparation and Characterization data of Carbon Dot .............................................S3
. Optimization of Conditions and General Procedure................................................S6
. Control Experiments and Spectroscopic Data .........................................................S8
. Characterization Data of All Products ...................................................................S10
1
13
19
. H, C and F NMR of All Products....................................................................S17
S1
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ChemSusChem
10.1002/cssc.202000277
1
. Materials and Methods
1
H NMR spectra were recorded using a Bruker Avance DPX 400 MHz instrument with
1
3
tetramethylsilane (TMS) as an internal standard. C NMR spectra were obtained at 101 MHz and
1
9
referenced to the internal solvent signals. F spectra were obtained at 377 MHz respectively. Mass
spectra were recorded using a Trio-2000 GC-MS spectrometer. UV-vis absorption spectra were
recorded with a U-3900 UV-vis spectrophotometer. Blue LEDs (3 W, λ = 440 ± 10 nm, 145 lm
@
700mA) were used as the irradiation light. Commercially available reagents and solvents were
used without further purification. TEM and HRTEM images were obtained by using JEOL
JEM-2100F transmission electron microscope at an acceleration voltage of 150 kV. XRD patterns
were obtained by using an X-ray diffractometer (Bruker, Germany) with Cu-Kα radiation (λ =
1.5178 Å). The 2θ scanning range was from 10° to 80° with a scanning speed of 0.1 °/s. The
–1
–1
FT-IR spectra (4000 cm to 400 cm ) in KBr were obtained using Varian Excalibur 3100 FT-IR
spectrometer. The Raman spectra performed on laser confocal micro-Raman Spectroscopy
(inVia-Reflex). Ultraviolet photoelectron spectroscopy (UPS) was performed on Thermo
Scientific ESCALab 250Xi. The gas discharge lamp was used for UPS, with Helium gas admitted
and the He I emission line at 21.22 eV employed. The Helium pressure in the analysis chamber
-8
during analysis is about 3×10 mbar.
S2
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10.1002/cssc.202000277
2
. Preparation and Characterization data of Carbon Dot
Preparation of Carbon Dot:
The carbon dot (CD) was prepared via ionothermal synthesis method. 0.1 M 2,6-diaminopyridine
and 0.6 M acrylic acid were added into 5.0 mL of ZnCl tetraethylene glycol solution (0.50 M)
2
and stirred at 100 °C for 1 h. Then reaction mixture was slowly raised to 210 °C and stirred for
another 4 h. After cooled down, the reaction solution was diluted with methanol. The supernatant
was collected after centrifugation and then shrunk by rotate evaporation to a volume of about 20
mL. Following precipitation in ethyl ether made the removal of residual ZnCl and afforded
2
products as dark brown solids (dilution and precipitation for three times).
Characterization data of CD:
Figure S1 TEM, HRTEM images and particle size distributions for CD (5.6±1.3 nm).
Figure S2 XRD patterns of CD (2θ, 22.4°; d-spacing, 3.91 Å).
S3
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10.1002/cssc.202000277
-1
-1
Figure S3 Raman spectra for CD. The spectra presented D band (1357 cm ), G band (1575 cm ).
Figure S4 XPS survey spectra for CD. The survey spectra indicated that CD consist of carbon (C
s, 285 eV), oxygen (O 1s, 532 eV) and nitrogen (N 1s, 400 eV) elements. The deconvolution of
1
the high-resolution XPS spectra (Figure S7) revealed C=C/C–C (284.7 eV), C–N (285.9 eV), C–
OH (286.2 eV), C=O (287.3 eV), COOH (288.7 eV), C=O (532.0 eV), C–O (533.3 eV), pyridinic
N (399.0 eV), pyrrolic N (400.1 eV) and graphitic N (401.2 eV) groups on the surface of CD.
S4
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10.1002/cssc.202000277
Figure S5 FT-IR spectra for CD. The FTIR spectra gave the definite characterization for the
−
1
−1
existence of functional groups, such as O−H (~3437 cm ), C−H (~2920 cm ), COOH (~1720
−
1
−1
−1
−1
cm ), C=O (~1624 cm ), C−N (~1429 cm ), and C−O−C (~1084 cm ). Apparently, there were
abundant hydrophilic O−H and COOH groups on the surface of CD, thereby ensuring their good
solubility in water.
Figure S6 UPS spectra for CD. We could calculate HOMO level of CD was –6.26 eV versus
vacuum level. According to the reference standard for which 0 V vs NHE equals –4.44 eV, the
valance band energy of CD to be 1.82 eV vs NHE. The bandgap energies could be estimated
according to the equation of 1240/λedge, where λedge was the onset value of the emissive peaks in
the direction of shorter wavelengths (λedge=450 nm). The calculated bandgap energy was 2.76 eV,
and the conduction band was -0.94 eV.
S5
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3
. Optimization of Conditions and General Procedure
[
a]
Table S1. The optimization of conditions.
[
a]
[b]
Entry
PC
Solvent
Yield (%)
56
1
2
3
4
5
6
7
8
9
1
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
Blue CD
-
CH
CH
CH
3
2
3
CN
Cl
OH
38
2
52
DMF
11
H
2
H
2
H
2
H
2
H
2
H
2
H
2
H
2
O
78
O/CH
O/CH
O/CH
O/CH
O/CH
O
CN (1:1)
CN (2:1)
CN (1:2)
CN (3:1)
CN (2:1)
66
3
3
3
3
3
87
83
81
[
c]
0
70
[
d]
11
None
None
[
e]
1
2
Blue CD
O
[
a] Reaction condition: 0.1 mmol 1a, 0.2 mmol 2a, 3 mg CD in 2.5 mL solvent, blue LEDs (λmax=440 nm)
1
irradiation at room temperature for 24 h, Ar. [b] H NMR yield with 2,2-diphenylacetonitrile as internal
standard. [c] 0.12 mmol 2a. [d] No CD. [e] No light.
S6
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General procedure for CD catalyzed borylation of diazonium salts
A 10 mL Pyrex tube equipped with a magnetic stir bar was charged with 0.1 mmol diazonium salts,
.2 mmol B pin , 3 mg CD, and 2.5 mL solvent (H O:CH CN =2:1 or H O). This system was
0
2
2
2
3
2
bubbled with Ar for 10 minutes, then sealed and irradiated at room temperature by blue LED for
4 hours. When reaction was finished, the mixture was evaporated to remove the solvent. The
2
residue was purified by flash chromatography on silica gel (eluting with hexane/ethyl acetate) to
afford the desired product.
S7
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4
. Control Experiments and Spectroscopic Data
Scheme S1. Radical trapping experiments for CD catalyzed borylation of diazonium salts
A 10 mL Pyrex tube equipped with a magnetic stir bar was charged with 0.1 mmol diazonium salts,
0
.2 mmol B pin , 3mg CD, TEMPO or MNP (0.2 mmol) and 2.5 mL solvent (H O:CH CN =2:1
2
2
2
3
or H O). This system was bubbled with Ar for 10 minutes, then sealed and irradiated at room
2
temperature by blue LED for 24 hours. When reaction was finished, the mixture was evaporated to
1
remove. The yield of product was detected by crude HNMR with 2,2-diphenylacetonitrile as
internal standard.
Table S2. Template reaction with different photocatalysts.
[
a]
[b]
Entry
PC
Solvent
Yield (%)
1
2
3
4
5
6
eosin Y
eosin Y
H
2
H
2
H
2
H
2
H
2
H
2
O/CH
3
3
3
CN (2:1)
CN (2:1)
CN (2:1)
75
72
77
57
85
73
O
Ir(ppy)
Ir(ppy)
O/CH
O
3
3
Ru(bpy)3Cl
Ru(bpy)3Cl
O/CH
O
2
2
[
a] Reaction condition: 0.1 mmol 1a, 0.2 mmol 2a, 3 mol % photosensitizer in 2.5 mL solvent, blue LEDs
1
(
λmax=440 nm) irradiation at room temperature for 24 h, Ar. [b] H NMR yield with 2,2-diphenylacetonitrile
S8
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10.1002/cssc.202000277
as internal standard.
Figure S7 Absorption spectra of blue CD, 1a (4-isopropylbenzenediazonium tetrafluoroborate),
-2
2
a (B pin ). [Blue CD] = 3.75×10 mg/mL. [1a] = 0.1 mM, [2a] = 0.2 mM.
2 2
Figure S8 a) Emission quenching of blue CD by 1a and 2a. b) Luminescence
quenching spectra of blue CD as a function of concentration of 1a. Inset is the Stern–
-2
Volmer plot of blue CD by 1a. [Blue CD] = 3.75×10 mg/mL. [1a] = 0.1 mM, [2a] =
0
.2 mM. excitation wavelength was 340 nm
S9
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5
. Characterization Data of All Products
2-(4-isopropylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3a):
1
White solid, yield: 82 %, H NMR (400 MHz, CD CN) δ 7.66 (d, J = 7.8 Hz, 2H), 7.29 (d, J = 7.9
3
1
3
Hz, 2H), 2.94 (hept, J = 6.9 Hz, 1H), 1.33 (s, 12H), 1.25 (d, J = 6.9 Hz, 6H). C NMR (101 MHz,
CD CN) δ 152.40, 134.62, 125.96, 83.64, 34.05, 24.21, 23.10. HRMS (EI) calculated for
3
+
C H BO [M] : 246.1786, Found:246.1794.
15
23
2
4,4,5,5-tetramethyl-2-(p-tolyl)-1,3,2-dioxaborolane (3b):
1
White solid, 77 %. H NMR (400 MHz, CD CN) δ 7.61 (d, J = 7.7 Hz, 2H), 7.21 (d, J = 7.7 Hz,
3
13
2
2
H), 2.35 (s, 3H), 1.31 (s, 12H). C NMR (101 MHz, CD CN) δ 141.54, 134.51, 128.55, 83.64,
3
+
4.23, 20.76. HRMS (EI) calculated for C H BO [M] : 218.1473, Found: 218.1482.
1
3
19
2
4,4,5,5-tetramethyl-2-(m-tolyl)-1,3,2-dioxaborolane (3c):
1
White solid, 58 %. H NMR (400 MHz, CD CN) δ 7.58 (s, 1H), 7.55 (d, J = 6.7 Hz, 1H), 7.34 (d,
3
1
3
J = 8.5 Hz, 1H), 7.31 (s, 1H), 2.38 (s, 3H), 1.35 (s, 12H). C NMR (101 MHz, CD CN) δ 137.30,
3
+
1
2
34.97, 131.96, 131.46, 127.81, 83.73, 24.24, 20.40. HRMS (EI) calculated for C H BO [M] :
1
3
19
2
18.1473, Found: 218.1479.
4,4,5,5-tetramethyl-2-(o-tolyl)-1,3,2-dioxaborolane (3d):
S10
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10.1002/cssc.202000277
1
Oil liquid, 54 %. H NMR (400 MHz, CD CN) δ 7.70 (d, J = 7.3 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H),
3
1
3
7
1
2
.27 – 7.14 (m, 2H), 2.53 (s, 3H), 1.37 (s, 12H). C NMR (101 MHz, CD CN) δ 144.48, 135.49,
3
+
30.78, 129.70, 124.74, 83.50, 24.24, 21.36. HRMS (EI) calculated for C H BO [M] :
1
3
19
2
18.1473, Found: 218.1481.
2-(4-(tert-butyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3e):
1
White solid, 81 %. H NMR (400 MHz, CD CN) δ 7.69 (d, J = 7.6 Hz, 2H), 7.47 (d, J = 7.6 Hz,
3
1
3
2
2
H), 1.35 (s, 21H). C NMR (101 MHz, CD CN) δ 154.50, 134.39, 124.79, 83.64, 34.50, 30.45,
3
+
4.24. HRMS (EI) calculated for C H BO [M] : 260.1942, Found: 260.1949.
16
25
2
4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (3f):
1
Oil liquid, 51 %. H NMR (400 MHz, CD CN) δ 7.78 (d, J = 7.4 Hz, 2H), 7.52 (t, J = 7.4 Hz, 1H).
3
3
1
7
8
.43 (t, J = 7.3 Hz, 2H), 1.36 (s, 12H). C NMR (101 MHz, CD CN) δ 134.47, 131.30, 127.85,
3
+
3.81, 24.34. HRMS (EI) calculated for C H BO [M] : 204.1316, Found: 204.1323.
1
2
17
2
2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3g):
1
Oil liquid, 82 %. H NMR (400 MHz, CD CN) δ 7.78 (d, J = 8.4 Hz, 2H), 7.04 (d, J = 8.5 Hz, 2H),
3
13
13
3
1
.91 (s, 3H), 1.42 (s, 12H). C NMR (101 MHz, CD CN) δ C NMR (101 MHz, CD3CN) δ
3
+
62.30, 136.24, 113.43, 83.54, 54.79, 24.25. HRMS (EI) calculated for C H BO [M] : 234.1422,
1
3
19
3
S11
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10.1002/cssc.202000277
Found:234.1429.
2-(3-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3h):
1
White solid, 62 %. H NMR (400 MHz, CD CN) δ 7.35 (d, J = 4.7 Hz, 2H), 7.28 (s, 1H), 7.10 –
3
1
3
7
.02 (m, 1H), 3.82 (s, 3H), 1.36 (s, 12H). C NMR (101 MHz, CD CN) δ 159.21, 129.14, 126.76,
3
+
1
18.79, 117.35, 83.86, 54.79, 24.29. HRMS (EI) calculated for C H BO [M] : 234.1422, Found:
1
3
19
3
234.1431.
2-(4-fluorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3i):
1
Oil liquid, 40 %. H NMR (400 MHz, CD CN) δ 7.75 (dd, J = 8.1, 6.5 Hz, 2H), 7.12 (t, J = 8.9 Hz,
3
13
2
H), 1.31 (s, 12H). C NMR (101 MHz, CD CN) δ 164.97 (d, J = 248.3 Hz), 136.86 (d, J = 8.3
3
9
1
Hz), 114.82 (d, J = 20.4 Hz), 83.98, 24.22. F NMR (377 MHz, CD CN) δ -63.57. HRMS (EI)
3
+
calculated for C H BFO [M] : 222.1222, Found: 222.1230.
12
16
2
2-(4-chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3j):
1
White solid, 68 %. H NMR (400 MHz, CD CN) δ 7.68 (d, J = 8.1 Hz, 2H), 7.39 (d, J = 8.2 Hz,
3
1
3
2
H), 1.32 (s, 12H). C NMR (101 MHz, CD CN) δ 137.00, 136.03, 128.03, 84.12, 24.20. HRMS
3
+
(
EI) calculated for C H BClO [M] : 238.0926, Found: 238.0930.
12
16
2
2-(3-chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3k):
S12
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ChemSusChem
10.1002/cssc.202000277
1
Oil liquid, 63 %. H NMR (400 MHz, CD CN) δ 7.70 (s, 1H), 7.66 (d, J = 7.3 Hz, 1H), 7.51 (d, J
3
1
3
=
8.0 Hz, 1H), 7.40 (t, J = 7.6 Hz, 1H), 1.35 (s, 12H). C NMR (101 MHz, CD CN) δ 133.89,
3
+
1
2
33.61, 132.63, 131.15, 129.75, 84.24, 24.23. HRMS (EI) calculated for C H BClO [M] :
1
2
16
2
38.0926, Found: 238.0929.
2-(2-chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3l):
1
Oil liquid, 49 %. H NMR (400 MHz, CD3CN) δ 7.68 (d, J = 7.3 Hz, 1H), 7.49-7.38 (m, 2H),
1
3
7
1
2
.34 (t, J = 7.1 Hz, 1H), 1.38 (s, 12H). C NMR (101 MHz, CD CN) δ 138.80, 136.25, 132.15,
3
+
29.28, 126.21, 84.21, 24.13. HRMS (EI) calculated for C H BClO [M] : 238.0926, Found:
1
2
16
2
38.0928.
2-(4-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3m):
1
White solid, 73 %. H NMR (400 MHz, CD CN) δ 7.61 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 8.1 Hz,
3
1
3
2
H), 1.31 (s, 12H). C NMR (101 MHz, CD CN) δ 136.20, 131.02, 125.65, 84.13, 24.23. HRMS
3
+
(
EI) calculated for C H BBrO [M] : 282.0421, Found: 282.0428.
12
16
2
2-(3-bromophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3n):
1
White solid, 52 %. H NMR (400 MHz, CD CN) δ 7.85 (s, 1H), 7.70 (d, J = 7.4 Hz, 1H), 7.67 (d,
3
1
3
J = 8.2 Hz, 1H), 7.35 (t, J = 7.7 Hz, 1H), 1.36 (s, 12H). C NMR (101 MHz, CD CN) δ 136.86,
3
S13
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ChemSusChem
10.1002/cssc.202000277
+
1
2
34.09, 132.99, 130.06, 121.96, 84.27, 24.20. HRMS (EI) calculated for C H BBrO [M] :
12 16 2
82.0421, Found: 282.0424.
methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (3o):
1
White solid, 59 %. H NMR (400 MHz, CD CN) δ 7.98 (d, J = 8.0 Hz, 2H), 7.81 (d, J = 8.0 Hz,
3
13
2
8
H), 3.88 (s, 3H), 1.33 (s, 12H). C NMR (101 MHz, CD CN) δ 166.63, 134.47, 132.56, 128.45,
3
+
4.28, 51.81, 24.22. HRMS (EI) calculated for C H BBrO [M] : 262.1371, Found:262.1378.
14
19
4
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (3p):
1
White solid, 81 %. H NMR (400 MHz, CD CN) δ 7.86 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 7.6 Hz,
3
1
3
2
H), 1.36 (s, 12H). C NMR (101 MHz, CD CN) δ 134.80, 131.40, 118.62, 114.34, 84.54, 24.20.
3
+
HRMS (EI) calculated for C H BNO [M] : 229.1269, Found: 229.1273.
13
16
2
4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (3q):
1
White solid, 52 %. H NMR (400 MHz, CD CN) δ 7.91 (d, J = 7.6 Hz, 2H), 7.72 (d, J = 7.7 Hz,
3
1
3
2
H), 1.38 (s, 12H). C NMR (101 MHz, CD CN) δ 134.89, 132.10 (q, J = 32.0 Hz), 124.39 (q, J
3
1
9
=
3.8 Hz), 124.37 (q, J = 272.5 Hz), 84.40, 24.19. F NMR (377 MHz, CD CN) δ -63.52. HRMS
3
+
(
EI) calculated for C H BF O [M] : 272.1190, Found: 272.1193.
13
16
3
2
4,4,5,5-tetramethyl-2-(4-nitrophenyl)-1,3,2-dioxaborolane (3r):
S14
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ChemSusChem
10.1002/cssc.202000277
1
White solid, 80 %. H NMR (400 MHz, CD CN) δ 8.23 (d, J = 7.9 Hz, 2H), 7.95 (d, J = 7.9 Hz,
3
1
3
2
H), 1.39 (s, 12H). C NMR (101 MHz, CD CN) δ 149.99, 135.39, 122.50, 84.69, 24.18. HRMS
3
(
EI) calculated for C H BNO [M]+: 249.1167, Found: 249.1171.
12 16 4
4,4,5,5-tetramethyl-2-(naphthalen-1-yl)-1,3,2-dioxaborolane (3s):
1
White solid, 62 %. H NMR (400 MHz, CD CN) δ 8.75 (d, J = 8.1 Hz, 1H), 8.13-7.99 (m, 2H),
3
1
3
7
1
.93 (d, J = 7.8 Hz, 1H), 7.62 – 7.50 (m, 3H), 1.45 (s, 12H). C NMR (101 MHz, CD CN) δ
3
36.71, 135.36, 133.25, 131.47, 128.35, 128.19, 126.25, 125.66, 125.10, 83.86, 24.28. HRMS (EI)
+
calculated for C H BO [M] : 254.1473, Found: 254.1477.
16
19
2
2-(4-isopropylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane (3t):
1
White solid, 35 %. H NMR (400 MHz, CDCl ) δ 7.73 (d, J = 7.5 Hz, 2H), 7.22 (d, J = 7.6 Hz,
3
1
3
2
H), 3.76 (s, 4H), 2.90 (hept, J = 6.8 Hz, 1H), 1.25 (d, J = 6.8 Hz, 6H), 1.01 (s, 6H). C NMR
(
101 MHz, CDCl ) δ 151.62, 134.07, 125.80, 72.32, 34.31, 31.91, 23.92, 21.94. HRMS (EI)
3
+
calculated for C H BO [M] : 232.1629, Found: 232.1626.
14
21
2
2-(4-isopropylphenyl)-4,4,6,6-tetramethyl-1,3,2-dioxaborinane (3u):
S15
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ChemSusChem
10.1002/cssc.202000277
1
White solid, 41 %. H NMR (400 MHz, CDCl ) δ 7.76 (d, J = 7.4 Hz, 2H), 7.20 (d, J = 7.4 Hz,
3
1
3
2
H), 2.90 (hept, J = 6.8 Hz, 1H), 1.89 (s, 2H), 1.40 (s, 12H), 1.24 (d, J = 6.8 Hz, 6H). C NMR
(
101 MHz, CDCl ) δ 151.33, 134.17, 125.72, 70.79, 49.30, 34.44, 32.01, 24.06. HRMS (EI)
3
+
calculated for C H BO [M] : 260.1942, Found: 260.1942.
16
25
2
2-(4-isopropylphenyl)-4,4,6-trimethyl-1,3,2-dioxaborinane (3v):
1
Oil liquid, 52 %. H NMR (400 MHz, CDCl ) δ 7.74 (d, J = 7.4 Hz, 2H), 7.20 (d, J = 7.4 Hz, 2H),
3
4
1
1
.39 – 4.26 (m, 1H), 2.89 (hept, J = 6.8 Hz, 1H), 1.89 – 1.80 (m, 1H), 1.56 (t, J = 12.6 Hz, 1H),
1
3
.39 – 1.30 (m, 9H), 1.24 (d, J = 6.9 Hz, 6H). C NMR (101 MHz, CDCl ) δ 151.36, 134.08,
3
25.73, 70.93, 65.01, 46.34, 34.41, 31.48, 28.30, 24.03, 23.40. HRMS (EI) calculated for
+
C H BO [M] : 246.1786, Found: 246.1784.
15
23
2
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. H, C and F NMR of All Products
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