A SO2F2 mediated mild, practical, and gram-scale dehydroxylative transforming primary alcohols to quaternary ammonium salts

Article abstract of DOI:10.1016/j.tet.2019.07.007

A simple, practical and gram-scale process for direct transformation of primary alcohols or silyl ethers to ammonium salts was developed. This method has the feathers of easy work-up (a simple filtration), mild condition, high yield, great practicality and robustness. And the application of the ammonium salts in Suzuki coupling reaction was also accomplished.

Full text of DOI:10.1016/j.tet.2019.07.007

Accepted Manuscript
A SO F mediated mild, practical, and gram-scale dehydroxylative transforming
2 2
primary alcohols to quaternary ammonium salts
Chuang Zhao, Gao-Feng Zha, Wan-Yin Fang, Njud S. Alharbi, Hua-Li Qin
PII:
S0040-4020(19)30749-5
https://doi.org/10.1016/j.tet.2019.07.007
TET 30449
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 May 2019
Revised Date: 3 July 2019
Accepted Date: 5 July 2019
Please cite this article as: Zhao C, Zha G-F, Fang W-Y, Alharbi NS, Qin H-L, A SO F mediated mild,
2 2
practical, and gram-scale dehydroxylative transforming primary alcohols to quaternary ammonium salts,
Tetrahedron (2019), doi: https://doi.org/10.1016/j.tet.2019.07.007.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
To create your abstract, type over the instructions in the template box below.
Fonts or abstract dimensions should not be changed or altered.
A SO2F2 mediated mild, practical, and gram-
scale dehydroxylative transforming primary
alcohols to quaternary ammonium salts
Leave this area blank for abstract info.
Chuang Zhaoa , Gao-Feng Zhaa, * , Wan-Yin Fanga , Njud S. Alharbib and Hua-Li Qina, *
a State Key Laboratory of Silicate Materials for Architectures; and School of Chemistry, Chemical Engineering
and Life Science, Wuhan University of Technology, Wuhan, Hubei Province 430070, People’s Republic of
China
b Biotechnology Research group, Deportment of Biological Sciences, Faculty of Science, King Abdulaziz
University, Jeddah, Saudi Arabia

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
A SO2F2 mediated mild, practical, and gram-scale dehydroxylative transforming
primary alcohols to quaternary ammonium salts
Chuang Zhaoa Gao-Feng Zha a, *, Wan-Yin Fanga , Njud S. Alharbib and Hua-Li Qina,
,
a State Key Laboratory of Silicate Materials for Architectures; and School of Chemistry, Chemical Engineering and Life Science, Wuhan University of
Technology, Wuhan, Hubei Province 430070, People’s Republic of China
b Biotechnology Research group, Deportment of Biological Sciences, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A simple, practical and gram-scale process for direct transformation of primary alcohols or silyl
ethers to ammonium salts was developed. This method has the feathers of easy work-up (a
simple filtration), mild condition, high yield, great practicality and robustness. And the
application of the ammonium salts in Suzuki coupling reaction was also accomplished.
Available online
2019 Elsevier Ltd. All rights reserved
.
Keywords:
ammonium salts
primary alcohols
silyl ethers
Suzuki coupling
dehydroxylative coupling
1. Introduction
Quaternary ammonium salts are ubiquitous and important
chemicals with many valuable industrial applications including
antimicrobial agents,1 surfactants,2 and antistatic agents.3 And
these onium salts play important roles in phase-transfer
catalysis,4 anion-exchange membranes,5 and asymmetric
catalysis.6 Besides, quaternary ammonium salts are also useful
intermediates in organic synthesis such as Hofmann elimination,7
Stevens rearrangement,8 and aza-Claisen rearrangement.9
Furthermore, aryltrimethylammonium salts are versatile building
blocks to participate in Kumada-Corriu cross-coupling,10 Suzuki
cross-coupling,11 Miyaura borylation12, Negishi cross-coupling,13
and Buchwald−Hartwig amination.14 Because of their
significance, the development of a mild, simple, and practical
methods for construction of ammonium salts from ready
available materials is of great importance and highly desirable.
Currently, numerous protocols have been reported for the
synthesis of quaternary ammonium salts, among which the
Menschutkin reaction involving a tertiary amine nucleophile
replacing a leaving group in an aliphatic or aromatic nucleophilic
substitution reaction is the most popular and predominating
processes (Scheme 1a).15 However, the available Menschutkin
reactions for the assembly of quaternary ammonium salts, mainly
relied on the use of either organic halides or active species of
sulfonates (tosylates, mesylates, triflates), which are not
Scheme 1. Synthesis of quaternary ammonium salts.
On the other hand, alcohols are a class of readily available,
inexpensive and abundant compounds from chemical industry,
coal tar, fuels and biomass.17 However, alcohols are usually
unreactive as leaving-group because the hydroxy group in an
alcohol molecule cannot be easily replaced by a nucleophilic
reagent. Therefore, alcohols have to be used in the forms of
halides, tosylates, triflates, and sulfonates, etc. to functionalize as
better leaving groups.18 It is of great significance to achieve
direct converting alcohols to quaternary ammonium salts for
further chemical transformation.7-14 Recently, sulfuryl fluoride
(SO2F2), another inexpensive (about 1 $/kg), abundant and
relatively inert electrophile (stable up to 400 ºC when dry), has
been widely used in SuFEx click chemistry and other versatile
manipulations.19 Based on the successful application of SO2F2 as
an electrophile to react with hydroxy groups of phenols for
generating fluorosulfates to participate in nucleophilic
substitutions and SuFEx click chemistry (Scheme 2a),19d-z we
envision that the hydroxy groups of alcohols would also proceed
environment friendly.16
———
Corresponding author. e-mail: zgflmx@whut.edu.cn (G.-F. Zha), qinhuali@whut.edu.cn (H.-L. Qin).

2
Tetrahedron
ACCEPTED MANUSCRIPT
nucleophilic reaction with SO2F2 to form the fluorosulfates,
which would provide their corresponding ammonium salts after
reacting with tertiary amines (Scheme 2b). Herein, we report a
mild, simple method for the assembly of quaternary ammonium
salts through SO2F2 mediated dehydroxylative coupling primary
alcohols with tertiary amines. (Scheme 1b).
Scheme 2. The SO2F2 mediated transforming hydroxy groups.
2. Results and discussion
Table 1. Optimization of the Reaction Conditions.a
Entry
2a (X equiv)
Solvent
Yield (3a, %)b
a Reaction conditions: SO2F2 (Toxic by inhalation. Operated in fume hoods)
was introduced by needle from a balloon filled with the gas to a mixture of
alcohols (1, 10 mmol), amine (2, 30 mmol) and PhCl (25 mL) at room
temperature for 12 h. b Isolated yield was obtained through direct filtration.
1.0
PhCl
48
1
2
2.0
3.0
3.0
3.0
PhCl
79
Table 3. Optimization of the reaction conditions of silyl ethers
with Et3N
PhCl
99
3
4c
MeCN
THF
66
80
5
a Reaction conditions: SO2F2 (Toxic by inhalation. Operated in fume hoods)
was introduced by needle from a balloon filled with the gas to a mixture of
PhCH2OH (1a, 10 mmol), Et3N (2a) and PhCl (25 mL) at room temperature
for 12 h. b Isolated yield was obtained through direct filtration. c The reaction
solution was concentrated and PhCl (20 mL) was added for crystallization.
Entry
RnSi(OEt)4-n
Si(OEt)4
Ratio (4:2a)
1:3
Yield (3r, %)b
1
2
3
4
5
6
7
33
36
27
16
39
76
99
Initially, we chose phenylmethanol (1a) and Et3N (2a) as
reaction partners and probed reaction conditions for the
envisioned conversion. To our delight, it was found that after
simply filtration, 48% isolated yield of the desired ammonium
product (3a) was obtained from the reaction of 1.0 equivalent of
alcohol 1a with 1.0 equivalent of 2a Et3N in PhCl under SO2F2
atmosphere (balloon) at room temperature for 6 h (Table 1, entry
1). Elevating the amine to 2.0 equivalent provided the
corresponding ammonium salt significantly to 79% (Table 1,
entry 2). Further condition screening revealed that 99% yield was
obtained when the loading of triethylamine was increased to 3.0
equivalent (Table 1, entry 3). Notably, PhCl was found to be the
best solvent for this reaction (Table 1, entry 3 compared with
entries 4 and 5, see supporting information for detail). Therefore,
the conditions of Table 1, entry 3 was chosen as the standard
procedure for examination of functional groups compatibility and
substrate scope.
MeSi(OEt)3
Me2Si(OEt)2
Me3Si(OEt)
MeSi(OEt)3
MeSi(OEt)3
MeSi(OEt)3
1:3
1:3
1:3
1:1.5
1:1
1.5:1
a Reaction conditions: SO2F2 (Toxic by inhalation. Operated in fume hoods)
was introduced by needle from a balloon filled with the gas to a mixture of
silyl ether (4), Et3N (2, 10 mmol) and PhCl (25 mL) at room temperature for
12 h. b Isolated yield was obtained through direct filtration.
Inspired by the successful transformation of primary alcohols
and the fact that silyl ethers have similar properties to alcohol to
react with SO2F2,19c we continued our study by examining the
reaction of silyl ethers 4 and Et3N 2a under the same conditions.
Interestingly, 33% yield of the desired product 3r was obtained
using the identical conditions for this transformation (Table 3,
entry 1). After screening a large variety of conditions (see
supporting information for details), we found that MeSi(OEt)3
was the best ether for formation of ammoniums comparing with
other counterparts (Table 3, entries 1-6). The reaction of 1.0
Table 2. Screening of substrate scope of alcohols.a,b

3
K3PO4 (3.0 eq.) and THF (10 mL) was allowed to stir at 60 oC for 12 h
equivalent of amine 2a with 1.5 equivalent of MeSi(OEt)3
generated the corresponding quaternary ammonium salt 3r in
nearly quantitative yield (Table 3, entry 7).
ACCEPTED MANUSCRIPT
under Argon atmosphere. b Isolated yields.
To test the utility of these ammonium salts, a Nickel catalyzed
Suzuki coupling reaction was developed for the synthesis of
corresponding diarylmethanes. The substrate scope and
functional group tolerance were shown in Table 5. It was worth
highlighting that the substrates of ammonium salts functionalized
with both electron-withdrawing groups and electron-donating
groups tolerated smoothly under the reaction conditions and the
products 6a-6e were obtained in good to excellent yields (yield
50% to 89%). The substrates of ammonium salts containing
naphthalene ring were also compatible to provide the
corresponding products 6f and 6g in 35% and 72% yields,
respectively. 6h, 6i, 6j and 6k was obtained in moderate to
quantitative yield (30%-97%) when ammonium salt 3a reacted
with corresponding boronic acids.
Table 4. Screening of substrate scope of amine with silyl
ethers.a,b
Scheme 3. Anion exchange reactions of the ammonium salts.
Subsequently, anion exchange reactions of the readily
available fluorosulfates 3 were examined for the construction of
quaternary ammonium salts of other anions. To our delight, when
the salts of KBF4 or KPF6 was used, the N-benzyl-N,N-
diethylethanaminium sulfofluoridate 3a was successfully
converted to the corresponding tetrafluoroborate or
hexafluorophosphate(V) in near quantitative yields (Scheme 3).
a Reaction conditions: SO2F2 (Toxic by inhalation. Operated in fume hoods)
was introduced by needle from a balloon filled with the gas to a mixture of
MeSi(OR1)3 (4, 15 mmol) Et3N (2, 10 mmol) and PhCl (25 mL) at room
temperature for 12 h. b Isolated yield was obtained through direct filtration.
Afterwards, many aliphatic tertiary amines were tested under
the optimized conditions to react with MeSi(OEt)3 4a for the
formation of quaternary ammonium salts (Table 4). Excitingly,
the corresponding ammonium salts were obtained in good to
excellent yields (3r, 3v-3y). Besides MeSi(OEt)3, the reaction of
MeSi(OMe)3 with many tertiary amines was also examined for
the construction of methylated ammonium salts (3z-3ag). In most
cases, satisfactory yields of the products (3z-3ac) were obtained.
However, 3ad and 3ae were generated in relatively low yields,
which indicated that the solubility and steric effect had
significant influence on the yields of the products. Surprisingly,
the sterically hindered ganglion blocker pempidine20 1af was
smoothly converted to the corresponding product 3af in 76%
yield. It was worth noting that the single dehydroxylative product
3ag was obtained in quantitative yield while no double
dehydroxylative product was observed. Ammonium salt 3a was
obtained in quantitative yield from the reaction of
MeSi(OBn)3with Et3N.
3. conclusions
In summary, a SO2F2 mediated dehydroxylative coupling of
primary alcohols or coupling of silyl ethers with amines for
gram-scale construction of ammonium salts was achieved with
high efficiency and broad substrate scope. The method has the
feathers of easy work-up (a simple filtration), mild condition,
high yield, great practicality and robustness. The application of
the ammonium salts in Suzuki coupling reaction was also
accomplished.
4. Experimental section
4.1. General considerations
All reactions were carried out in dried glassware. All reagents
were purchased from commercial sources and used without
further purification. Unless otherwise specified, NMR spectra
Table 5. Suzuki cross-coupling of ammonium salts.a,b
1
were recorded in CDCl3 or DMSO-d6 on a 500 MHz (for H),
471 MHz (for 19F), 126 MHz (for 13C) spectrometer. All chemical
shifts were reported in ppm relative to TMS (1H NMR, 0 ppm) as
internal standards. The HPLC experiments were carried out on a
Waters e2695 instrument (column: J&K, RP-C18, 5 ꢀm, 4.6 ×
150 mm), and the yields of the products were determined by
using the corresponding pure compounds as the external
standards. The coupling constants were reported in Hertz (Hz).
The following abbreviations were used to explain the
multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet, br = broad. MS experiments were performed on a
TOF-Q ESI or CI/EI instrument. Melting points were measured
and uncorrected.
4.2. Preparation of substrates.
a Reaction conditions: a mixture of ammonium salts (3, 1.0 mmol), aryl
boronic acid (5, 1.2 mmol, 1.2 eq.), Ni(OTf)3 (5 mol%), DPPB (10 mol%),
MeSi(OBn)3 was prepared according to the literature.21
(3s,5s,7s)-N,N-dimethyladamantan-1-amine 2x was prepared

4
Tetrahedron
ACCEPTED MANUSCRIPT
according to the literature.22 N,N-dimethyl-3-phenylpropan-1-
White solid (2.19 g from (2-methoxyphenyl)methanol and
amine 2ac was prepared according to the literature.23 All
homemade starting materials are identical to those reported
regarding the 1H and 13C NMR and melting points (if applicable).
triethylamine, isolated yield 68%). M.p. 93-95 oC. 1H NMR (500
MHz, DMSO-d6) δ 7.52 (t, J = 7.6 Hz, 1H), 7.46 (d, J = 7.6 Hz,
1H), 7.17 (d, J = 8.4 Hz, 1H), 7.06 (t, J = 7.6 Hz, 1H), 4.42 (s,
2H), 3.86 (s, 3H), 3.18 (q, J = 7.2 Hz, 6H), 1.29 (t, J = 7.1 Hz,
9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126
MHz, DMSO-d6) δ 158.9, 134.4, 132.3, 120.7, 115.9, 112.0, 55.6,
55.2, 52.4, 7.7. HRMS (ESI+) [M-OSO2F]+ calculated m/z for
[C14H24NO]+: 222.1852, found: 222.1849.
4.3. General procedure for synthesis of fluorosulfate salt from
primary alcohol and tertiary amine.
To an oven-dried reaction flask (100 mL) with stirring bar
charged with primary alcohol (1, 10 mmol), EtN3 (2a, 30 mmol,
3.0 equiv, 3.04 g) and PhCl (25 mL), the tube was then sealed
with a septum, SO2F2 gas (sulfuryl fluoride) was introduced by
needle (the inside diameter was 1.5 mm) from a balloon filled
with the gas (degassed with SO2F2 for 10~30 seconds). The
reaction mixture was vigorously stirred at room temperature, and
a solid precipitate was formed after about one hour in most
examples. With vigorous stirring for 12 h, the precipitate was
washed with PhCl (2 mL × 3) and dried in vacuo to yield the title
compound as a solid.
4.3.6. N,N-diethyl-N-(3-
methoxybenzyl)ethanaminium sulfofluoridate 3f.
White solid (2.80 g from (3-methoxyphenyl)methanol and
o
1
triethylamine, isolated yield 87%). M.p. 104-106 C. H NMR
(500 MHz, DMSO-d6) δ 7.43 (t, J = 7.8 Hz, 1H), 7.12-7.08 (m,
3H), 4.43 (s, 2H), 3.80 (s, 3H), 3.19 (q, J = 7.2 Hz, 6H), 1.31 (t, J
= 7.2 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR
(126 MHz, DMSO-d6) δ 159.4, 130.2, 129.1, 124.5, 118.2, 115.6,
59.5, 55.2, 52.2, 7.4. HRMS (ESI+) [M-OSO2F]+ calculated m/z
for [C14H24NO]+: 222.1852, found: 222.1849.
4.3.1. N-benzyl-N,N-diethylethanaminium
sulfofluoridate 3a.
White solid (2.88 g from phenylmethanol and triethylamine,
isolated yield 99%; 2.89 g from MeSi(OBn)3 and trimethylamine,
isolated yield 99%). M.p. 134-136 C. H NMR (500 MHz,
DMSO-d6) δ 7.52 (m, 5H), 4.47 (s, 2H), 3.17 (q, J = 7.2 Hz, 6H),
1.31 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.1.
13C NMR (126 MHz, DMSO-d6) δ 132.5, 130.2, 129.1, 127.8,
59.5, 52.0, 7.4. HRMS (ESI+) [M-OSO2F]+ calculated m/z for
[C13H22N]+: 192.1747, found: 192.1448.
4.3.7. N,N-diethyl-N-(4-
(methylthio)benzyl)ethanaminium sulfofluoridate 3g.
White solid. (1.89 g from (4-(methylthio)phenyl)methanol and
triethylamine, isolated yield 56%). M.p. 96-98 oC. 1H NMR (500
MHz, DMSO-d6) δ 7.44 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.3 Hz,
2H), 4.43 (s, 2H), 3.16 (q, J = 7.2 Hz, 6H), 2.51 (s, 3H), 1.30 (t, J
= 7.1 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C NMR
(126 MHz, DMSO-d6) δ 141.2, 132.8, 125.7, 123.7, 59.2, 51.9,
14.1 (d, J = 1.8 Hz), 7.4. HRMS (ESI+) [M-OSO2F]+ calculated
m/z for [C14H24NS]+: 238.1624, found: 238.1623.
o
1
4.3.2. N-([1,1'-biphenyl] -2-ylmethyl)-N,N-
diethylethanaminium sulfofluoridate 3b.
4.3.8. N-(4-(benzyloxy)benzyl)-N,N-
diethylethanaminium sulfofluoridate 3h.
White solid (3.01 g from [1,1'-biphenyl]-2-ylmethanol and
o
1
triethylamine, isolated yield 82%). M.p. 141-143 C. H NMR
(CDCl3, 500 MHz) δ 7.69 (d, J = 7.8 Hz, 1H), 7.62 (t, J = 7.5 Hz,
1H), 7.55-7.52 (m, 3H), 7.47 (t, J = 7.3 Hz, 1H), 7.43 (d, J = 7.3
Hz, 2H), 7.39 (d, J = 7.5 Hz, 1H), 4.56 (s, 2H), 2.95 (q, J = 7.2
Hz, 6H), 0.92 (t, J = 7.2 Hz, 9H). 19F NMR (CDCl3, 471MHz) δ
40.0. 13C NMR (126 MHz, DMSO-d6) δ 144.9, 139.8, 134.1,
131.5, 130.5, 129.7, 129.0, 127.9, 127.8, 124.9, 56.7, 52.3, 7.2.
HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C19H26N]+:
268.2060, found: 268.2056.
White solid. (2.11 g from (4-(benzyloxy)phenyl)methanol and
o
1
triethylamine, isolated yield 53%). M.p. 122-124 C. H NMR
(500 MHz, DMSO-d6) δ 7.48-7.39 (m, 6H), 7.35 (t, J = 7.2 Hz,
1H), 7.14 (d, J = 8.7 Hz, 2H), 5.15 (s, 2H), 4.40 (s, 2H), 3.13 (q,
J = 7.2 Hz, 6H), 1.30 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz,
DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ 159.6,
136.7, 134.0, 128.5, 128.0, 127.8, 119.7, 115.2, 69.4, 59.0, 51.6,
7.4. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C20H28NO]+:
298.2165, found: 298.2163.
4.3.3. N-([1,1'-biphenyl] -4-ylmethyl)-N,N-
diethylethanaminium sulfofluoridate (3c).
4.3.9. N,N-diethyl-N-(3-
phenoxybenzyl)ethanaminium sulfofluoridate 3i.
White solid (2.83 g from [1,1'-biphenyl]-4-ylmethanol and
triethylamine, isolated yield 77%). M.p. 91-93 oC. 1H NMR (500
MHz, DMSO-d6) δ 7.81 (d, J = 7.7 Hz, 2H), 7.73 (d, J = 7.5 Hz,
2H), 7.61 (d, J = 7.8 Hz, 2H), 7.51 (t, J = 7.4 Hz, 2H), 7.42 (t, J =
7.1 Hz, 1H), 4.52 (s, 2H), 3.20 (q, J = 7.0 Hz, 6H), 1.34 (t, J =
6.9 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C NMR
(126 MHz, DMSO-d6) δ 141.7, 138.9, 133.1, 129.1, 128.1, 127.1,
126.82, 126.77, 59.2, 52.0, 7.5. HRMS (ESI+) [M-OSO2F]+
calculated m/z for [C19H26N]+: 268.2060, found: 268.2056.
White solid (2.99 g from (3-phenoxyphenyl)methanol and
o
1
triethylamine, isolated yield 78%). M.p. 126-128 C. H NMR
(500 MHz, DMSO-d6) δ 7.53 (t, J = 8.0 Hz, 1H), 7.45-7.41 (m,
2H), 7.28 (d, J = 7.7 Hz, 1H), 7.21-7.15 (m, 3H), 7.10-7.08 (m,
2H), 4.46 (s, 2H), 3.18 (q, J = 7.2 Hz, 6H), 1.27 (t, J = 7.2 Hz,
9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126
MHz, DMSO-d6) δ 157.1, 156.1, 130.7, 130.2, 129.7, 127.3,
124.0, 122.2, 120.2, 118.9, 59.1, 52.1, 7.4. HRMS (ESI+) [M-
OSO2F]+ calculated m/z for [C19H26NO]+: 284.2009, found:
284.2008.
4.3.4. N,N-diethyl-N-(4-methylbenzyl)ethanaminium
sulfofluoridate 3d.
4.3.10. N,N-diethyl-N-(2-nitrobenzyl)ethanaminium
White solid (2.99 g from p-tolylmethanol and triethylamine,
isolated yield 98%). M.p. 64-66 oC. 1H NMR (500 MHz, DMSO-
d6) δ 7.40 (d, J = 7.9 Hz, 2H), 7.32 (d, J = 7.9 Hz, 2H), 4.42 (s,
2H), 3.14 (q, J = 7.2 Hz, 6H), 2.35 (s, 3H), 1.30 (t, J = 7.1 Hz,
9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126
MHz, DMSO-d6) δ 139.9, 132.4, 129.6, 124.7, 59.3, 51.8, 20.7,
7.4. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C14H24N]+:
206.1903, found: 206.1900.
sulfofluoridate 3j.
White solid (2.56 g from (2-nitrophenyl)methanol and
o
1
triethylamine, isolated yield 76%). M.p. 98-100 C. H NMR
(500 MHz, DMSO-d6) δ 8.13 (dd, J = 8.0 Hz, J = 1.2 Hz, 1H),
7.90-7-80 (m, 3H), 4.82 (s, 2H), 3.25 (q, J = 7.2 Hz, 6H), 1.24 (t,
J = 7.2 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C
NMR (126 MHz, DMSO-d6) δ 151.2, 135.8, 133.8, 132.3, 125.8,
121.1, 55.1, 53.0, 7.6. HRMS (ESI+) [M-OSO2F]+ calculated m/z
for [C13H21N2O2]+: 237.1598, found: 237.1595.
4.3.5. N,N-diethyl-N-(2-
methoxybenzyl)ethanaminium sulfofluoridate 3e.

5
OSO2F]+ calculated m/z for [C17H24N]+: 242.1903, found:
242.1901.
4.3.11. N,N-diethyl-N-(4-nitrobenzyl)ethanaminium
sulfofluoridate 3k.
ACCEPTED MANUSCRIPT
White solid (2.99 g from (4-nitrophenyl)methanol and
4.3.17. N,N-diethyl-N-methylethanaminium
sulfofluoridate 3q.
o
1
triethylamine, isolated yield 89%). M.p. 174-175 C. H NMR
(500 MHz, DMSO-d6) δ 8.33 (d, J = 8.7 Hz, 2H), 7.83 (d, J = 8.7
Hz, 2H), 4.64 (s, 2H), 3.22 (q, J = 7.2 Hz, 6H), 1.33 (t, J = 7.2 Hz,
9H). 19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126
MHz, DMSO-d6) δ 148.5, 134.9, 134.1, 123.8, 58.3, 52.5, 7.4.
HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C13H21N2O2]+:
237.1598, found: 237.1595.
White solid (2.02 g from methanol and triethylamine, isolated
o
1
yield 94%). M.p. 194-196 C. H NMR (500 MHz, DMSO-d6) δ
3.25 (q, J = 7.2 Hz, 6H), 2.88 (s, 3H), 1.19 (t, J = 7.0 Hz, 9H). 19F
NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126 MHz,
DMSO-d6) δ 55.0 (t, J = 2.7 Hz), 45.9 (t, J = 3.6 Hz), 7.4. HRMS
(ESI+) [M-OSO2F]+ calculated m/z for [C7H18N]+: 116.1434,
found: 116.1433.
4.3.12. N-(4-cyanobenzyl)-N,N-diethylethanaminium
sulfofluoridate 3l.
4.3.18. Tetraethylammonium sulfofluoridate 3r.
White solid. (2.15 g from 4-(hydroxymethyl)benzonitrile and
o
1
White solid (1.90 g from ethanol and trimethylamine, isolated
yield 83%; 2.26 g from MeSi(OEt)3 and triethylamine, isolated
triethylamine, isolated yield 68%). M.p. 161-163 C. H NMR
(500 MHz, DMSO-d6) δ 7.98 (d, J = 8.3 Hz, 2H), 7.73 (d, J = 8.2
Hz, 2H), 4.57 (s, 2H), 3.20 (q, J = 7.2 Hz, 6H), 1.31 (t, J = 7.2 Hz,
9H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C NMR (126
MHz, DMSO-d6) δ 133.6, 133.1, 132.8, 118.2, 113.0, 58.7, 52.4,
7.5. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C14H21N2]+:
217.1699, found: 217.1695.
o
1
yield 99%). M.p. 298-300 C. H NMR (500 MHz, DMSO-d6) δ
3.20 (q, J = 7.3Hz, 8H), 1.16 (td, J = 7.2 Hz, J = 1.4 Hz, 12H).
19F NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126 MHz,
DMSO-d6) δ 51.4 (t, J = 3.6 Hz), 7.0. HRMS (ESI+) [M-
OSO2F]+ calculated m/z for [C8H20N]+: 130.1590, found:
130.1587.
4.3.13. N,N-diethyl-N-(2-iodobenzyl)ethanaminium
sulfofluoridate 3m.
4.3.19. N,N,N-triethyl-2-phenylethanaminium
sulfofluoridate 3s.
White solid (2.29 g from (2-iodophenyl)methanol and
o
1
White solid (2.03 g from 2-phenylethanol and triethylamine,
triethylamine, isolated yield 55%). M.p. 132-134 C. H NMR
(CDCl3, 500 MHz) δ 8.07 (d, J = 7.7 Hz, 1H), 7.60 (dd, J = 7.7
Hz, J = 1.4 Hz, 1H), 7.55 (t, J = 7.7 Hz, 1H), 4.60 (s, 2H), 3.36 (q,
J = 7.2 Hz, 6H), 1.28 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz,
DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ 140.9,
133.9, 132.1, 131.1, 129.1, 105.2, 64.2, 53.3, 7.9. HRMS (ESI+)
[M-OSO2F]+ calculated m/z for [C13H21IN]+: 318.0713, found:
318.0710.
o
1
isolated yield 66%). M.p. 103-105 C. H NMR (500 MHz,
DMSO-d6) δ 7.38-7.34 (m, 4H), 7.30-7.28 (m, 1H), 3.37-3.32 (m,
8H), 2.98-2.95 (m, 2H), 1.23 (t, J = 7.1 Hz, 9H). 19F NMR (471
MHz, DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ
136.4, 129.0, 128.7, 127.0, 56.8, 52.1, 27.3, 7.2. HRMS (ESI+)
[M-OSO2F]+ calculated m/z for [C14H24N]+: 206.1903, found:
206.1901.
4.3.20. N,N,N-triethylprop-2-en-1-aminium
sulfofluoridate 3t.
4.3.14. N-(benzo[d][1,3]dioxol-5-ylmethyl)-N,N-
diethylethanaminium sulfofluoridate 3n.
White solid (2.07 g from prop-2-en-1-ol and triethylamine,
White solid (2.22 g from benzo[d][1,3]dioxol-5-ylmethanol
o
1
o
1
isolated yield 86%). M.p. 184-186 C. H NMR (500 MHz,
DMSO-d6) δ 6.03-5.95 (m, 1H), 5.67 (d, J = 16.7 Hz, 1H), 5.59
(d, J = 10.2 Hz, 1H), 3.86 (d, J = 7.0 Hz, 2H), 3.21 (q, J = 7.2 Hz,
6H), 1.20 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ
40.0. 13C NMR (126 MHz, DMSO-d6) δ 126.9, 125.5, 58.6, 52.1,
7.1. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C9H20N]+:
142.1590, found: 142.1587.
and triethylamine, isolated yield 66%). M.p. 132-134 C. H
NMR (500 MHz, DMSO-d6) δ 7.06 (s, 1H), 7.04 (d, J = 8.1 Hz,
1H), 7.01 (dd, J = 8.1 Hz, J = 1.2 Hz, 1H), 6.10 (s, 2H), 4.36 (s,
2H), 3.15 (q, J = 7.2 Hz, 6H), 1.28 (t, J = 7.2 Hz, 9H). 19F NMR
(471 MHz, DMSO-d6) δ 40.0. 13C NMR (126 MHz, DMSO-d6) δ
148.7, 147.7, 126.9, 120.9, 112.1, 108.6, 101.6, 59.6, 51.8, 7.4.
HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C14H22NO2]+:
236.1645, found: 236.1642.
4.3.21. N,N,N-triethylbut-3-yn-1-aminium
sulfofluoridate 3u.
4.3.15. N,N-diethyl-N-(naphthalen-1-
ylmethyl)ethanaminium sulfofluoridate 3o.
White solid (1.30 g from but-3-yn-1-ol and triethylamine,
o
1
isolated yield 51%). M.p. 156-158 C. H NMR (500 MHz,
DMSO-d6) δ 3.37-3.34 (m, 2H), 3.27 (q, J = 7.2 Hz, 6H), 3.08 (s,
1H), 2.70-2.68 (m, 2H), 1.17 (t, J = 7.2 Hz, 9H). 19F NMR (471
MHz, DMSO-d6) δ 40.0. 13C NMR (126 MHz, DMSO-d6) δ 79.5,
73.7, 53.8, 52.2, 12.0, 7.2. HRMS (ESI+) [M-OSO2F]+ calculated
m/z for [C10H20N]+: 154.1590, found: 154.1587.
White solid. (2.32 g from naphthalen-1-ylmethanol and
o
1
triethylamine, isolated yield 68%). M.p. 126-128 C. H NMR
(500 MHz, DMSO-d6) δ 8.43 (d, J = 8.6 Hz, 1H), 8.13 (d, J = 8.0
Hz, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.79 (d, J = 7.1 Hz, 1H), 7.71
(t, J = 7.5 Hz, 1H), 7.66-7.62 (m, 2H), 5.00 (s, 2H), 3.35 (q, J =
7.2 Hz, 6H), 1.24 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz,
DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ 133.5,
132.81, 132.80, 131.2, 129.1, 127.4, 126.3, 125.2, 124.3, 123.4,
58.0, 53.1, 7.9. HRMS (ESI+) [M-OSO2F]+ calculated m/z for
[C17H24N]+: 242.1903, found: 242.1901.
4.4. General procedure for synthesis of fluorosulfate salt from
silyl ether and tertiary amine.
To an oven-dried reaction flask (100 mL) with stirring bar
charged with tertiary amine (2, 10 mmol), MeSi(OR1)3 (15 mmol,
1.5 equiv) and PhCl (25 mL), the tube was then sealed with a
septum, SO2F2 gas (sulfuryl fluoride) was introduced by needle
(the inside diameter was 1.5 mm) from a balloon filled with the
gas (degassed with SO2F2 for 10~30 seconds). The reaction
mixture was vigorously stirred at room temperature, and a solid
precipitate was formed after about one hour in most examples.
With vigorous stirring for 12 h, the precipitate was washed with
4.3.16. 1-Benzyl-4-(benzyloxy)benzene 3p.
White solid (2.59 g from naphthalen-2-ylmethanol and
o
1
triethylamine, isolated yield 76%). M.p. 107-109 C. H NMR
(500 MHz, DMSO-d6) δ 8.12 (s, 1H), 8.06-8.00 (m, 3H), 7.65-
7.60 (m, 3H), 4.64 (s, 2H), 3.23 (q, J = 7.2 Hz, 6H), 1.36 (t, J =
7.2 Hz, 9H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C NMR
(126 MHz, DMSO-d6) δ 133.2, 132.8, 132.5, 128.9, 128.5, 128.3,
127.54, 127.53, 126.8, 125.3, 59.7, 52.1, 7.5. HRMS (ESI+) [M-

6
Tetrahedron
4.4.7. N-cyclohexyl-N,N-
PhCl (2 mL × 3) and dried in vacuo to yield the title compound
ACCEPTED MANUSCRIPT
dimethylcyclohexanaminium sulfofluoridate 3ab.
as a white solid.
White solid (2.94 g from MeSi(OMe)3 and N-cyclohexyl-N-
methylcyclohexanamine, isolated yield 95%). M.p. 186-188 C.
4.4.1. N-ethyl-N,N-dipropylpropan-1-aminium
sulfofluoridate 3v.
o
1H NMR (500 MHz, DMSO-d6) δ 3.51-3.46 (m, 2H), 2.80 (s,
6H), 2.09-2.07 (m, 4H), 1.85-1.83 (m, 4H), 1.61-1.58 (m, 2H),
1.49-1.42 (m, 4H), 1.38-1.30 (m, 4H), 1.17-1.09 (m, 2H). 19F
NMR (471 MHz, DMSO-d6) δ 40.0. 13C NMR (126 MHz,
DMSO-d6) δ 69.6, 43.2 (t, J = 3.7 Hz), 25.5, 25.0, 24.6. HRMS
(ESI+) [M-OSO2F]+ calculated m/z for [C14H28N]+: 210.2216,
found: 210.2212.
White solid (1.47 g from MeSi(OEt)3 and tripropylamine,
o
1
isolated yield 54%). M.p. 192-194 C. H NMR (500 MHz,
CDCl3) δ 3.34 (q, J = 7.3 Hz, 2H), 3.16-3.12 (m, 6H), 1.72-1.64
(m, 6H), 1.30 (t, J = 7.0 Hz, 3H), 0.99 (t, J = 7.4 Hz, 9H). 19F
NMR (471 MHz, CDCl3) δ 38.4. 13C NMR (126 MHz, CDCl3) δ
59.9 (t, J = 2.7 Hz), 54.3 (t, J = 2.7 Hz), 15.4, 10.7, 7.7. HRMS
(ESI+) [M-OSO2F]+ calculated m/z for [C11H26N]+: 172.2060,
found: 172.2057.
4.4.8. N,N,N-trimethyl-3-phenylpropan-1-aminium
sulfofluoridate 3ac.
4.4.2. 1-cyclohexyl-1-ethylpiperidin-1-ium
sulfofluoridate 3w.
White solid (1.90 g from MeSi(OMe)3 and N,N-dimethyl-3-
o
1
phenylpropan-1-amine, isolated yield 68%). M.p. 95-97 C. H
NMR (500 MHz, DMSO-d6) δ 7.32 (t, J = 7.5 Hz, 2H), 7.27 (d, J
= 7.3 Hz, 1H), 7.22 (t, J = 7.2 Hz, 2H), 3.33-3.30 (m, 2H), 3.05
(s, 9H), 2.61 (t, J = 7.8 Hz, 2H), 2.05-1.98 (m, 2H). 19F NMR
(471 MHz, DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ
140.3, 128.5, 128.3, 126.2, 65.1 (t, J = 2.7 Hz), 52.3 (t, J = 3.7
Hz), 31.7, 23.9. HRMS (ESI+) [M-OSO2F]+ calculated m/z for
[C12H20N]+: 178.1590, found: 178.1587.
White solid (2.11
g
from MeSi(OEt)3 and 1-
o 1
cyclohexylpiperidine, isolated yield 82%). M.p. 196-198 C. H
NMR (500 MHz, DMSO-d6) δ 3.45-3.31 (m, 6H), 3.23-3.20 (m,
2H), 2.07-2.05 (m, 2H), 1.86-1.76 (m, 6H), 1.61-1.43 (m, 5H),
1.40-1.32 (m, 2H), 1.18 (t, J = 7.1 Hz, 3H). 19F NMR (471 MHz,
DMSO-d6) δ 40.0. 13C NMR (126 MHz, DMSO-d6) δ 67.6, 53.7,
49.5, 25.1, 24.9, 24.6, 20.5, 18.8, 7.3. HRMS (ESI+) [M-
OSO2F]+ calculated m/z for [C13H26N]+: 196.2060, found:
196.2058.
4.4.9. 4,4-Dimethylmorpholin-4-ium sulfofluoridate
3ad.
4.4.3. (3s,5s,7s)-N-ethyl-N,N-dimethyladamantan-1-
White solid (0.55
g
from MeSi(OMe)3 and 4-
o 1
aminium sulfofluoridate 3x.
methylmorpholine, isolated yield 25%). M.p. 239-241 C. H
NMR (500 MHz, DMSO-d6) δ 3.90 (s, 4H), 3.40 (t, J = 4.8 Hz,
4H), 3.17 (s, 6H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C
NMR (126 MHz, DMSO-d6) δ 60.3, 60.0, 50.9. HRMS (ESI+)
[M-OSO2F]+ calculated m/z for [C6H14NO]+: 116.1070, found:
116.1068.
White solid (2.51 g from MeSi(OEt)3 and (3s,5s,7s)-N,N-
dimethyladamantan-1-amine, isolated yield 82%). M.p. 218-220
1
oC. H NMR (500 MHz, DMSO-d6) δ 3.27 (q, J = 7.1 Hz, 2H),
2.78 (s, 6H), 2.22 (s, 3H), 2.02-2.01 (m, 6H), 1.66-1.60 (m, 6H),
1.27 (t, J = 7.0 Hz, 3H). 19F NMR (471 MHz, DMSO-d6) δ 40.0.
13C NMR (126 MHz, DMSO-d6) δ 73.7, 52.6 (t, J = 2.7 Hz), 42.5
(t, J = 3.7 Hz), 34.6, 33.8, 29.8, 8.4. HRMS (ESI+) [M-OSO2F]+
calculated m/z for [C14H26N]+: 208.2060, found: 208.2058.
4.4.10. (1s,4s)-1-methyl-3-oxoquinuclidin-1-ium
sulfofluoridate 3ae.
White solid (0.72
g from MeSi(OMe)3 and (1s,4s)-
o 1
4.4.4. N-(3,5-dimethoxybenzyl)-N,N-
diethylethanaminium sulfofluoridate 3y.
quinuclidin-3-one, isolated yield 30%). M.p. 206-208 C. H
NMR (500 MHz, DMSO-d6) δ 4.23 (s, 2H), 3.70-3.64 (m, 2H),
3.57-3.51 (m, 2H), 3.10 (s, 3H), 2.71-2.70 (m, 1H), 2.28-2.22 (m,
2H), 2.11-2.06 (m, 2H). 19F NMR (471 MHz, DMSO-d6) δ 40.1.
13C NMR (126 MHz, DMSO-d6) δ 203.1, 67.0, 56.1, 51.1, 36.5,
20.9. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C8H14NO]+:
140.1070, found: 140.1068.
White solid (3.41
g
from MeSi(OEt)3 and N-(3,5-
dimethoxybenzyl)-N-ethylethanamine, isolated yield 97%). M.p.
o
1
175-177 C. H NMR (500 MHz, DMSO-d6) δ 6.67 (t, J = 2.1
Hz, 1H), 6.652-6.647 (m, 2H), 4.38 (s, 2H), 3.79 (s, 6H), 3.20 (q,
J = 7.2 Hz, 6H), 1.30 (t, J = 7.2 Hz, 9H). 19F NMR (471 MHz,
DMSO-d6) δ 40.0. 13C NMR (126 MHz, DMSO-d6) δ 160.6,
129.7, 110.6, 101.5, 59.7, 55.4, 52.3, 7.5. HRMS (ESI+) [M-
OSO2F]+ calculated m/z for [C15H26NO2]+: 252.1958, found:
252.1955.
4.4.11. 1,1,2,2,6,6-hexamethylpiperidin-1-ium
sulfofluoridate 3af.
White solid (2.05 g from MeSi(OMe)3 and 1,2,2,6,6-
pentamethylpiperidine, isolated yield 76%). M.p. 194-196 oC. 1H
NMR (500 MHz, DMSO-d6) δ 2.93 (s, 6H), 1.86-1.84 (m, 4H),
1.70-1.64 (m, 2H), 1.51 (s, 12H). 19F NMR (471 MHz, DMSO-
d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ 74.0, 42.5 (t, J =
3.7 Hz), 33.8, 26.2, 15.3. HRMS (ESI+) [M-OSO2F]+ calculated
m/z for [C11H24N]+: 170.1903, found: 170.1901.
4.4.5. Tetramethylammonium sulfofluoridate 3z.
White solid (1.73 g from MeSi(OMe)3 and trimethylamine,
1
isolated yield 99%). M.p. >300 oC. H NMR (500 MHz, DMSO-
d6) δ 3.09 (s, 12H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C
NMR (126 MHz, DMSO-d6) δ 54.4 (t, J = 3.7 Hz). HRMS
(ESI+) [M-OSO2F]+ calculated m/z for [C4H12N]+: 74.0964,
found: 74.0962.
4.4.12. 2-(Dimethylamino)-N,N,N-
trimethylethanaminium sulfofluoridate 3ag.
4.4.6. N,N,N-trimethylcyclohexanaminium
sulfofluoridate 3aa.
White solid (2.38 g from MeSi(OMe)3 and N1,N1,N2,N2-
tetramethylethane-1,2-diamine, isolated yield 97%). M.p. 95-96
White solid (2.35
g
from MeSi(OMe)3 and N,N-
1
oC. H NMR (500 MHz, DMSO-d6) δ 3.41 (t, J = 7.2 Hz, 2H),
dimethylcyclohexanamine, isolated yield 98%). M.p. 175-177 oC.
1H NMR (500 MHz, DMSO-d6) δ 3.27 (tt, J = 11.8 Hz, J = 2.9
Hz, 1H), 2.99 (s, 9H), 2.14-2.12 (m, 2H), 1.87-1.85 (m, 2H),
1.61-1.58 (m, 1H), 1.43-1.35 (m, 2H), 1.30-1.22 (m, 2H), 1.15-
1.06 (m, 1H). 19F NMR (471 MHz, DMSO-d6) δ 40.1. 13C NMR
(126 MHz, DMSO-d6) δ 73.1, 50.2 (t, J = 3.6 Hz), 25.5, 24.8,
24.3. HRMS (ESI+) [M-OSO2F]+ calculated m/z for [C9H20N]+:
142.1590, found: 142.1587.
3.09 (s, 9H), 2.64-2.62 (m, 2H), 2.19 (s, 6H). 19F NMR (471
MHz, DMSO-d6) δ 40.1. 13C NMR (126 MHz, DMSO-d6) δ 61.8
(t, J = 3.7 Hz), 52.73 (t, J = 4.5 Hz), 52.70, 44.9. HRMS (ESI+)
[M-OSO2F]+ calculated m/z for [C7H19N2]+: 131.1543, found:
131.1539.
4.5. General procedure for synthesis of diarylmethane from
fluorosulfate salt and aryl boric acid.

7
A mixture of ammonium salts (3, 1.0 mmol), boronic acid (5,
White solid (175.2 mg from N,N-diethyl-N-(naphthalen-2-
ACCEPTED MANUSCRIPT
1.2 mmol, 1.2 eq.), Ni(OTf)2 (5 mol %, 17.8 mg), DPPB (10 mol
%, 42.6 mg), K3PO4 (3.0 mmol, 636 mg, 3.0 eq.) and THF (10
mL) was allowed to react for 12 h under Argon atmosphere
ylmethyl)ethanaminium
sulfofluoridate
and
(4-
cyanophenyl)boronic acid, isolated yield 72%). The NMR data is
identical to that reported in literature.11b 1H NMR (CDCl3, 500
MHz) δ 7.83-7.78 (m, 3H), 7.62 (s, 1H), 7.59 (d, J = 8.1 Hz, 2H),
7.50-7.45 (m, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.27-7.26 (m, 1H),
4.20 (s, 2H).
o
(balloon) at 60 C. Subsequently, the mixture was diluted with
water (50 mL) and extracted with EtOAc (3×10 mL). The
combined organic layer was washed with brine (25 mL), dried
over anhydrous Na2SO4, and concentrated to dryness. The residue
was purified by silica gel chromatography through gradient
elution with EtOAc / Petroleum ether to afford pure products (6).
4.5.8. Diphenylmethane 6h.
Colorless
oil
(149.8
mg
from
N-benzyl-N,N-
diethylethanaminium sulfofluoridate and phenylboronic acid,
isolated yield 89%). The NMR data is identical to that reported in
literature.25 1H NMR (CDCl3, 500 MHz) δ 7.33-7.30 (m, 4H),
7.24-7.21 (m, 6H), 4.02 (s, 2H).
4.5.1. 4-Benzylbenzonitrile 6a.
White
solid
(171.9
mg
from
N-benzyl-N,N-
diethylethanaminium sulfofluoridate and (4-cyanophenyl)boronic
o
acid, isolated yield 89%). M.p. 42-44 C. The NMR data is
4.5.9. 4-Benzyl-1,1'-biphenyl 6i.
identical to that reported in literature.11b 1H NMR (CDCl3, 500
MHz) δ 7.58 (d, J = 8.2 Hz, 2H), 7.36-7.24 (m, 5H), 7.18 (d, J =
7.2 Hz, 2H), 4.05 (s, 2H).
White
solid
(73.3
mg
from
N-benzyl-N,N-
diethylethanaminium sulfofluoridate and [1,1'-biphenyl]-4-
ylboronic acid, isolated yield 57%). The NMR data is identical to
that reported in literature.26 1H NMR (CDCl3, 500 MHz) δ 7.61
(d, J = 7.6 Hz, 2H), 7.56 (d, J = 7.9 Hz, 2H), 7.48-7.44 (m, 2H),
7.38-7.24 (m, 8H), 4.07 (s, 2H).
4.5.2. 4-(4-(Trifluoromethyl)benzyl)benzonitrile 6b.
Light yellow liquid (130.7 mg from N,N-diethyl-N-(4-
(trifluoromethyl)benzyl)ethanaminium
ammonium salt was obtained
sulfofluoridate
from
(this
(4-
4.5.10. 1-Benzyl-4-fluorobenzene 6j.
(trifluoromethyl)phenyl)methanol and triethylamine and used
directly without further purification) and (4-cyanophenyl)boronic
acid, isolated yield 50%). The NMR data is identical to that
reported in literature.11b 1H NMR (CDCl3, 500 MHz) δ 7.60-7.56
(m, 4H), 7.28 (d, J = 8.1 Hz, 4H), 4.10 (s, 2H). 19F NMR (CDCl3,
471MHz) δ -62.5 (s, 3F).
Slightly yellow oil (141.6 mg from N-benzyl-N,N-
diethylethanaminium sulfofluoridate and (4-fluorophenyl)boronic
acid, isolated yield 76%). The NMR data is identical to that
reported in literature.25 1H NMR (CDCl3, 500 MHz) δ 7.31 (t, J =
7.5 Hz, 2H), 7.24-7.12 (m, 5H), 6.99 (t, J = 8.5 Hz, 2H), 3.97 (s,
2H). 19F NMR (CDCl3, 471MHz) δ -116.2 (s, 1F).
4.5.3. 4-(4-Methylbenzyl)benzonitrile 6c.
4.5.11. 3-Benzylthiophene 6k.
Yellow liquid (170.0 mg from N,N-diethyl-N-(4-
Colorless
oil.
(169.0
mg
from
N-benzyl-N,N-
methylbenzyl)ethanaminium
sulfofluoridate
and
(4-
diethylethanaminium sulfofluoridate and thiophen-3-ylboronic
acid, isolated yield 97%). The NMR data is identical to that
reported in literature.27 1H NMR (CDCl3, 500 MHz) δ 7.35-7.31
(m, 2H), 7.28-7.23 (m, 4H), 6.95-6.94 (m, 2H), 4.01 (s, 2H).
cyanophenyl)boronic acid, isolated yield 82%). The NMR data is
identical to that reported in literature.11b 1H NMR (CDCl3, 500
MHz) δ 7.57 (d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 7.14
(d, J = 7.9 Hz, 2H), 7.06 (d, J = 7.9 Hz, 2H), 4.00 (s, 2H), 2.34
(s, 3H).
4.6. General procedure for anion exchange reactions of the
ammonium salts.
4.5.4. 4-(4-(Methylthio)benzyl)benzonitrile 6d.
White
solid
(131.6
mg
from
N,N-diethyl-N-(4-
KBF4 (3.15 g, 25 mmol) or KPF6 (4.60 g, 25 mmol) was
dissolved in 15 ml of H2O. N-benzyl-N,N-diethylethanaminium
sulfofluoridate 3a (7.28 g, 25 mmol) was dissolved in 25 ml of
CH2Cl2 and added to the aqueous solution of KBF4 or KPF6.
After stirring for 24 h at room temperature, the organic phase was
separated and washed with 10 ml of water dried over anhydrous
Na2SO4 and filtered. The filtrate was concentrated on a rotary
evaporator to obtain a white solid. The obtained solid was dried
in vacuo for 4 h.
(methylthio)benzyl)ethanaminium sulfofluoridate and (4-
o
cyanophenyl)boronic acid, isolated yield 55%). M.p. 69-71 C.
The NMR data is identical to that reported in literature.24 1H
NMR (CDCl3, 500 MHz) δ 7.57 (d, J = 8.2 Hz, 2H), 7.27 (d, J =
7.5 Hz, 2H), 7.21 (d, J = 8.3 Hz, 2H), 7.08 (d, J = 8.3 Hz, 2H),
3.99 (s, 2H), 2.47 (s, 3H).
4.5.5. 4-([1,1'-biphenyl] -4-ylmethyl)benzonitrile
6e.
White solid (150.7 mg from N-([1,1'-biphenyl]-4-ylmethyl)-
4.6.1. N-benzyl-N,N-diethylethanaminium
N,N-diethylethanaminium
sulfofluoridate
and
(4-
tetrafluoroborate 7a.
o
cyanophenyl)boronic acid, isolated yield 56%). M.p. 56-58 C.
The NMR data is identical to that reported in literature.11b 1H
NMR (CDCl3, 500 MHz) δ 7.61-7.54 (m, 6H), 7.44 (d, J = 7.5
Hz, 2H), 7.36-7.32 (m, 3H), 7.24 (d, J = 7.8 Hz, 2H), 4.08 (s,
2H).
White solid (6.63 g, isolated yield 95%). The NMR
data is identical to that reported in literature.28 1H NMR (DMSO-
d6) δ 7.53-7.52 (m, 5H), 4.47 (s, 2H), 3.16 (q, J = 7.2 Hz, 6H),
1.31 (t, J = 7.2 Hz, 9H). 19F NMR (DMSO-d6) -148.3.
4.6.2. N-benzyl-N,N-diethylethanaminium
hexafluorophosphate(V) 7b.
4.5.6. 4-(Naphthalen-1-ylmethyl)benzonitrile 6f.
White solid (85.2 mg from N,N-diethyl-N-(naphthalen-1-
White solid (8.26 g, isolated yield 98%). The NMR data is
identical to that reported in literature.29 1H NMR (DMSO-d6) δ
7.53-7.51 (m, 5H), 4.47 (s, 2H), 3.16 (q, J = 7.2 Hz, 6H), 1.31 (t,
J = 7.2 Hz, 9H). 19F NMR (DMSO-d6) -70.9.
ylmethyl)ethanaminium
sulfofluoridate
and
(4-
o
cyanophenyl)boronic acid, isolated yield 35%). M.p. 80-82 C.
The NMR data is identical to that reported in literature.11b 1H
NMR (CDCl3, 500 MHz) δ 7.91-7.86 (m, 2H), 7.83 (d, J = 8.2
Hz, 1H), 7.54-7.45 (m, 5H), 7.32 (d, J = 6.9 Hz, 1H), 7.28 (d, J =
7.9 Hz, 2H), 4.49 (s, 2H).
Acknowledgments
We are grateful to the National Natural Science Foundation of
China (Grant No. 21772150), the Wuhan applied fundamental
4.5.7. 4-(Naphthalen-2-ylmethyl)benzonitrile 6g.

8
Tetrahedron
ACCEPTED MANUSCRIPT
T.; Shoda, S.-I.; Watanabe, Y. Chem. Lett. 1977, 4, 383–386; f)
research plan of Wuhan Science and Technology Bureau (grant
Benazza, T.; Uzan, R.; Beaupere, D.; Demailly, G. Tetrahedron
Lett. 1992, 33, 4901–4904; g) Benazza, T.; Uzan, R.; Beaupere, D.;
Demailly, G. Tetrahedron Lett. 1992, 33, 3129–3132; h) Kelly, B.
D.; Lambert, T. H. J. Am. Chem. Soc. 2009, 131,13930–13931; i)
Dai, C.; Narayanam, J. M. R.; Stephenson, C. R. J. Nat. Chem.
2011, 3, 140-145
NO. 2017060201010216), the 111 Project (No. B18038) and Wuhan
University of Technology for the financial support.
References and notes
17. a) The Merck Index: An Encyclopedia of Chemicals, Drugs, and
Biologicals, 11th ed., Merck, Rahway, NJ, 1989, ISBN
091191028X, pp. 1138. b) Rahimi, A.; Azarpira, A.; Kim, H.;
Ralph, J.; Stahl, S. S. J. Am. Chem. Soc. 2013, 135, 6415-6418; c)
Vispute, T. P.; Zhang, H.; Sanna, A.; Xiao, R.; Huber, G. W.
Science 2010, 330, 1222-1227; d) Barta, K.; Ford, P. C. Acc.
Chem. Res. 2014, 47, 1503-1512; e) Tuck, C. O.; Perez, E.;
Horvath, I. T.; Sheldon, R. A.; Poliakoff, M. Science 2012, 337,
695-699.
1. a) Muñoz-Bonilla, A.; Fernández-Garcia, M. Prog. Polym. Sci.
2012, 37, 281-339; b) Jennings, M. C.; Minbiole, K. P. C.; Wuest,
W. M. ACS Infect. Dis. 2015, 1, 288-303.
2. a) Branzoi, V.; Branzoi, F.; Baibarac, M. Mater. Chem. Phys.
2000, 65, 288-297; b) Fuchs-Godec, R. The adsorption, Colloids
Surf., A 2006, 280, 130-139.
3. a) Hong, J. W.; Kim, H. K.; Yu, J. A.; Kim, Y. B. J. Appl. Polym.
Sci. 2002, 84, 132-137; b) Kuang, M.; Zhou, S.; Lei, J.; Li, Q. J.
Appl. Polym. Sci. 2008, 109, 3887-3891.
18. Alonso, F.; Foubelo, F.; González-Gómez, J. C.; Martínez, R.;
Ramón, D. J.; Riente, P.; Yus, M. Mol. Divers. 2010, 14, 411-424.
19. Sulfuryl fluoride (SO2F2) has been produced annually at more than
3 million kilograms per year since 2000, with a price as low as
$1/kg. see: a) Sulbaek Andersen, M. P.; Blake, D. R.; Rowland, F.
S.; Hurley, M. D.; Wallington, T. J. Environ. Sci. Technol. 2009,
43, 1067-1070. For reviews of SO2F2 utilization, see: b) Revathi,
L.; Ravindar, L.; Leng, J.; Rakesh, K. P.; Qin, H.-L. Asian J. Org.
Chem. 2018, 7, 662-682; c) Dong, J.; Krasnova, L.; Finn, M. G.;
Sharpless, K. B. Angew. Chem. Int. Ed. 2014, 53, 9430-9448. For
examples of SO2F2 in SuFEx click chemistry, see: d) Wang, H.;
Zhou, F.; Ren, G.; Zheng, Q.; Chen, H.; Gao, B.; Klivansky, L.;
Liu, Y.; Wu, B.; Xu, Q.; Lu, J.; Sharpless, K. B.; Wu, P. Angew.
Chem. Int. Ed. 2017, 56, 11203-11208; e) Gao, B.; Zhang, L.;
Zheng, Q.; Zhou, F.; Klivansky, L. M.; Lu, J.; Liu, Y.; Dong, J.;
Wu, P.; Sharpless, K. B. Nat. Chem. 2017, 9, 1083-1088; f) Liu,
Z.; Li, J.; Li, S.; Li, G.; Sharpless, K. B.; Wu, P. J. Am. Chem. Soc.
2018, 140, 2919-2925; g) Zhao, Q.; Ouyang, X.; Wan, X.;
Gajiwala, K. S.; Kath, J. C.; Jones, L. H.; Burlingame, A. L.;
Taunton, J. J. Am. Chem. Soc. 2017, 139, 680-685; h) Mortenson,
D. E.; Brighty, G. J.; Plate, L.; Bare, G.; Chen, W.; Li, S.; Wang,
H.; Cravatt, B. F.; Forli, S.; Powers, E. T.; Sharpless, K. B.;
Wilson, I. A.; Kelly, J. W. J. Am. Chem. Soc. 2018, 140, 200-210;
i) Wang, N.; Yang, B.; Fu, C.; Zhu, H.; Zheng, F.; Kobayashi, T.;
Liu, J.; Li, S.; Ma, C.; Wang, P. G.; Wang, Q.; Wang, L. J. Am.
Chem. Soc. 2018, 140, 4995-4999; j) Chen, W.; Dong, J.; Plate, L.;
Mortenson, D. E.; Brighty, G. J.; Li, S.; Liu, Y.; Galmozzi, A.;
Lee, P. S.; Hulce, J. J.; Cravatt, B. F.; Saez, E.; Powers, E. T.;
Wilson, I. A.; Sharpless, K. B.; Kelly, J. W. J. Am. Chem. Soc.
2016, 138, 7353-7364. For some selected examples of using SO2F2
in chemical transformations, see: k) Hanley, P. S.; Clark, T. P.;
Krasovskiy, A. L.; Ober, M. S.; O’Brien, J. P.; Staton, T. S. ACS
Catal. 2016, 6, 3515-3519; l) Schimler, S. D.; Cismesia, M. A.;
Hanley, P. S.; Froese, R. D. J.; Jansma, M. J.; Bland, D. C.;
Sanford, M. S. J. Am. Chem. Soc. 2017, 139, 1452-1455; m)
Epifanov, M.; Foth, P. J.; Gu, F.; Barrillon, C.; Kanani, S. S.;
Higman, C. S.; Hein, J. E.; Sammis, G. M. J. Am. Chem. Soc.
2018, 140, 16464-16468; n) Fang, W.-Y.; Leng, J.; Qin, H.-L.
Chem. Asian J. 2017, 12, 2323-2331; o) Wang, X.-Y.; Leng, J.;
Wang, S.-M.; Asiri, A. M.; Marwani, H. M.; Qin, H.-L.
Tetrahedron Lett. 2017, 58, 2340-2343; p) Fang, W.-Y.; Huang,
Y.-M.; Leng, J.; Qin, H.-L. Asian J. Org. Chem. 2018, 7, 751-756;
q) Zhao, C.; Fang, W.-Y.; Rakesh, K. P.; Qin, H.-L. Org. Chem.
Front. 2018, 5, 1835-1839; r) Zha, G.-F.; Fang, W.-Y.; Li, Y.-G.;
Leng, J.; Chen, X.; Qin, H.-L. J. Am. Chem. Soc. 2018, 140,
17666-17673; s) Zhao, C.; Zha, G.-F.; Fang W. Y.; Qin, H.-L. Eur.
J. Org. Chem. 2019, 1801-1807; t) Lekkala, R.; Lekkala, R.;
Moku, B.; Qin, H.-L. Org. Chem. Front. 2019, 6, 796-800; u)
Zhang, X.; Rakesh, K. P.; Qin, H.-L. Chem. Commun. 2019, 55,
2845-2848; v) Zha, G.-F.; Fang, W.-Y.; Leng, J.; Qin, H.-L. Adv.
Synth. Catal. 2019, 361, 2262-2267; w) Fang, W.-Y.; Qin, H.-L. J.
Org. Chem. 2019, 84, 5803-5812; x) Wang, S.-M.; Zhao, C.;
Zhang, X.; Qin, H. L. Org. Biomol. Chem. 2019, 17, 4087-4101; y)
Jiang, Y.; Sun, B.; Fang, W.-Y.; Qin, H.-L. Eur. J. Org. Chem.
2019, 3190-3194; z) Lekkala, R.; Lekkala, R.; Moku, B.; Rakesh,
K. P.; Qin, H.-L. Beilstein J. Org. Chem. 2019, 15, 976-980.
Note, sulfuryl fluoride is a neurotoxic gas and also a particularly
potent greenhouse gas, please handle with care in fume hoods.
20. Black, I. B. J. Neurochem. 1973, 20, 1265-1267.
4. a) Corey, E. J.; Xu, F.; Noe, M. C. J. Am. Chem. Soc. 1997, 119,
12414-12415; b) Asymmetric Phase Transfer Catalyst; Maruoka,
K., Ed.; WileyVCH: Weinheim, 2008. c) Zong, L. Tan, C.-H. Acc.
Chem. Res. 2017, 50, 842-856.
5. a) Varcoe, J. R.; Slade, R. C. T. Fuel Cells 2005, 5, 187-200; b)
Varcoe, J. R.; Atanassov, P.; Dekel, D. R.; Herring, A. M.;
Hickner, M. A.; Kohl, P. A.; Kucernak, A. R.; Mustain, W. E.;
Nijmeijer, K.; Scott, K.; Xu, T.; Zhuang, L. Energy Environ. Sci.
2014, 7, 3135-3191.
6. Qian, D.; Sun, J. Chem. Eur. J. 2019, 25, 3740-3751. And the
references therein.
7. a) Karmakar, R.; Yun, S. Y.; Wang, K.-P.; Lee, D. Org. Lett. 2014,
16, 6-9; b) Sato, Y.; Aoyama, T.; Shirai, H. J. Organomet. Chem.
1974, 82, 21-27.
8. a) Pine, S. H. Org. React. 1970, 18, 403-464; b) Lepley, A. R.;
Becker, R. H.; Giumanni, A. G. J. Org. Chem. 1971, 36,
12221227; c) Okazaki, S.; Shirai, N.; Sato, Y. J. Org. Chem. 1990,
55, 334-337; d) Tanaka, T.; Shirai, N.; Sugimori, J.; Sato, Y. J.
Org. Chem. 1992, 57, 5034-5036; e) Tayama, E.; Kimura, H.
Angew. Chem. Int. Ed. 2007, 46, 8869-8871.
9. Cant, A. A.; Bertrand, G. H. V.; Henderson, J. L.; Roberts, L.;
Greaney, M. F. Angew. Chem. Int. Ed. 2009, 48, 5199-5202.
10. a) Wenkert, E.; Han, A.-L.; Jenny, C.-J. J. Chem. Soc., Chem.
Commun. 1988, 975-976; b) Aresta, M.; Dibenedetto, A.;
Quaranta, E.; Lanfranchi, M.; Tiripicchio, A. Organometallics
2000, 19, 4199-4207; c) Reeves, J. T.; Fandrick, D. R.; Tan, Z.;
Song, J. J.; Lee, H.; Yee, N. K.; Senanayake, C. H. Org. Lett. 2010,
12, 4388-4391; d) Guo, W.-J.; Wang, Z.-X. Tetrahedron 2013, 69,
9580-9585.
11. a) Blakey, S. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003,
125, 6046-6047; b) Wang, T.; Yang, S.; Xu, S.; Han, C.; Guo, G.;
Zhao, J. RSC Adv. 2017, 7, 15805-15808; c) Maity, P.; Shacklady-
McAtee, D. M.; Yap, G. P. A.; Sirianni, E. R.; Watson, M. P. J.
Am. Chem. Soc. 2013, 135, 280-285.
12. a) Zhang, H.; Hagihara, S.; Itami, K. Chem. Eur. J. 2015, 21,
16796-16800; b) Hu, J.; Sun, H.; Cai, W.; Pu, X.; Zhang, Y.; Shi,
Z. J. Org. Chem. 2016, 81, 14-24; c) Basch, C. H.; Cobb, K. M.;
Watson, M. P. Org. Lett. 2016, 18, 136-139.
13. a) Xie, L.-G.; Wang, Z.-X. Angew. Chem., Int. Ed. 2011, 50,
4901-4904; b) Zhang, X.-Q.; Wang, Z.-X. J. Org. Chem. 2012, 77,
3658-3663.
14. Zhang, X.-Q.; Wang, Z.-X. Org. Biomol. Chem. 2014, 12, 1448-
1453.
15. a) Menschutkin, N.; Vasileff, M. Z. Phys. Chem. 1890, 5, 589-600;
b) Menschutkin, N. Z. Phys. Chem. 1890, 6, 41-57; c) Harman, D.;
Stewart, T. D.; Ruben, S. J. Am. Chem. Soc. 1942, 64, 2293-2294;
d) Hamann, S. D.; Teplitzky, D. R. Discuss. Faraday Soc. 1956,
22, 114-121; e) A. P. Harris, K. E. Weale, J. Chem. Soc. 1961, 146.
f) Henderson Jr., W. A.; Schultz, C. J. J. Org. Chem. 1962, 27,
4643-4646; g) Reinheimer, J. D.; Harley, J. D.; Meyers, W. W. J.
Org. Chem. 1963, 28, 1575-1579; h) Sommer, H. Z.; Jackson, L. L.
J. Org. Chem. 1970, 35, 1558-1562; i) Sommer, H. Z.; Lipp, H. I.;
Jackson, L. L. J. Org. Chem. 1971, 36, 824-828; j) Taft, R. W.;
Pienta, N. J.; Kamlet, M. J.; Arnett, E. M. J. Org. Chem. 1981, 46,
661-667; k) Wang, T.-T.; Lou, Q.-L. Chem. Eng. J. 2002, 87, 197-
206; l) Purse, B. W.; Gissot, A.; Rebek, J. J. Am. Chem. Soc. 2005,
127, 11222-11223; m) Stanger, K. J.; Lee, J.-J.; Smith, B. D. J.
Org. Chem. 2007, 72, 9663-9668.
16. a) Larock, R. C. Comprehensive Organic Transformations 2nd
edn, 689 (John Wiley & Sons, 1999); b) Weiss, R. G.; Snyder, E. I.
J. Chem. Soc. Chem. Commun. 1968, 21, 1358-1359; c) Weiss, R.
G.; Snyder, E. I. J. Org. Chem. 1972, 36, 403-406; d) Fujisawa, T.;
Iida, S.; Sato, T. Chem. Lett. 1984, 13, 1173–1174; e) Mukaiyama,
21. Igarashi, M.; Kubo, K.; Matsumoto, T.; Sato, K.; Ando, W.;
Shimada, S. RSC Adv. 2014, 4, 19099-19102.
22. Baxter, E. W.; Reitz, A. B. in Org. React. John Wiley & Sons, Inc.,
Hoboken, NJ, USA, 2002, pp. 1–714.

9
23. Sunada, Y.; Kawakami, H.; Imaoka, T.; Motoyama, Y.;
29. Kryshtal, G. V.; Zhdankina, G. M.; Zlotin, S. G. Eur. J. Org.
Chem. 2005, 2822-2827.
ACCEPTED MANUSCRIPT
Nagashima, H. Angew. Chem. Int. Ed. 2009, 48, 9511-9514.
24. Benischke, A. D.; Knoll, I.; Rerat, A.; Gosmini, C.; Knochel, P.
Chem. Commun. 2016, 52, 3171-3174.
25. Vasilopoulos, A.; Zultanski, S. L.; Stahl, S. S. J. Am. Chem. Soc.
2017, 139, 7705-7708.
Supplementary Material
26. Whitaker, L.; Harb, H. Y.; Pulis, A. P. Chem. Commun. 2017, 53,
9364-9367.
27. Tang, J.; Lv, L.; Dai, X.-J.; Li, C.-C.; Li, L.; Li, C.-J. Chem.
Commun. 2018, 54, 1750-1753.
Click here to remove instruction text...
28. Kryshtal, G. V.; Zhdankina, G. M.; Zlotin, S. G. Eur. J. Org.
Chem. 2008, 1777-1782.

ACCEPTED MANUSCRIPT
Highlights
1. A simple, practical and gram-scale process for direct transformation of primary
alcohols or silyl ethers to ammonium salts
2. This method has the feathers of easy work-up (a simple filtration), mild condition,
high yield, great practicality and robustness.
3. the application of the ammonium salts in Suzuki coupling reaction was also
accomplished.