Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction

Article abstract of DOI:10.1021/acs.joc.8b00262

The electrophilic ipso-substitution of trimethylsilyl-substituted benzene derivatives into nitrosobenzene derivatives is reported. The optimization of the reaction conditions was performed for moderately electron-deficient, electron-rich, and sterically hindered starting materials by varying reaction time, temperature, and equivalents of NOBF₄. Also, a stable intermediate of the nitrosation reaction could be characterized by ¹⁹F NMR which can be assigned to a NO⁺ adduct with the nitrosobenzene derivative. This complex decomposes upon aqueous workup and liberates the desired nitrosobenzene derivative.

Full text of DOI:10.1021/acs.joc.8b00262

Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE
Article
Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction
Corinna Kohlmeyer, Maike Klüppel, and Gerhard Hilt
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00262 • Publication Date (Web): 27 Feb 2018
Downloaded from http://pubs.acs.org on March 2, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.
The Journal of Organic Chemistry is published by the American Chemical Society.
1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction
a,b
b
a,
Corinna Kohlmeyer, Maike Klüppel and Gerhard Hilt *
a) Institut für Chemie, Universität Oldenburg, Carl-von-Ossietzky-Straße 9-11, 26111
Oldenburg, Germany
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
b) Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043
Marburg, Germany
Email: Gerhard.Hilt@uni-oldenburg.de
Abstract
The electrophilic ipso-substitution of trimethylsilyl-substituted benzene derivatives into
nitrosobenzene derivatives is reported. The optimization of the reaction conditions was
performed for moderately electron-deficient, electron-rich and sterically hindered starting
materials by varying reaction time, temperature and equivalents of NOBF . Also, a stable
4
19
intermediate of the nitrosation reaction could be characterized by F NMR which can be
+
assigned to a NO adduct with the nitrosobenzene derivative. This complex decomposes upon
aqueous workup and liberates the desired nitrosobenzene derivative.
Introduction
Aromatic nitroso compounds are a class of compounds of high importance in organic synthesis
1
as they are applied in various transformations, such as Diels-Alder reactions, nitroso-ene
2
3
4
5
reactions, nitroso-aldol reactions, allylborations or the addition of Grignard reagents.
6
7
Recently, several asymmetric and catalytic methods have been examined. Therefore, the
development of novel synthetic approaches for nitrosoarenes is still an important field in
8
organic chemistry. Their synthesis is most often accomplished by oxidation of the
9
10
corresponding aniline derivate using peracids, oxone or H
2
2
O as oxidant and various metal
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 2 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
peroxo complexes as catalyst.11 Alternatively, nitrosoarenes can be synthesized by direct
12
13
nitrosation using suitable nitrosating agents for in situ formation or a nitrosonium salt, such
as NOBF , as electrophile for electrophilic substitution. However, this method is limited to
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
electron-rich arenes such as anisole derivatives. In a seminal work, Molander extended this
synthetic strategy to a broad range of arenes by introducing potassium trifluoroborate as leaving
group which allowed the electrophile to attack in the ipso-position forming a nitrosoarene with
1
4
a defined regioselectivity (Scheme 1). Using a slight excess of NOBF , the reaction conditions
4
are very mild, and compatible with various functional groups. In addition to potassium
trifluoroborate, also a limited number of transformations with a trimethylsilyl group is known
1
5
to act as directing group to introduce a nitroso group. Based on this we were interested
reacting trimethylsilyl-substituted arenes with NOBF to synthesize nitrosoarenes. Similar to
the aryl trifluoroborates, trimethylsilyl-substituted arenes are cost-efficient and convenient to
4
1
6
synthesize, as they are readily accessible from the corresponding aryl bromide. An alternative
synthetic approach to trimethylsilyl-substituted arenes is the cobalt-catalyzed Diels-Alder
1
7
reaction that has been on our scientific agenda for a long time. Recently, we reported a related
reaction to the proposed synthesis of nitrosoarenes – a trimethylsilyl iodine exchange reaction
which demonstrated the suitability of the trimethylsilyl group as directing group in electrophilic
1
8
substitution reactions. We were able to develop a protocol for the chemical as well as for the
1
9
electrochemical version of these iodination reactions. This prompted us to examine a
nitrosodesilylation reaction using NOBF as an electrophile.
4
ACS Paragon Plus Environment

Page 3 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
SCHEME 1. Nitrosoarene synthesis via ipso-substitution reaction.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Results and Discussion
As of the investigation for suitable conditions for a nitrosodesilylation reaction, we chose
4
-methoxyphenyltrimethylsilane (1) as screening substrate since it is readily available and the
2
0
corresponding product is well described in literature. As the nitrosonium source we chose
2
1
NOBF
4
, because it is commercially available and easy to handle. Promisingly, in a first test
reaction (Scheme 2) quantitative conversion of the starting material could be achieved resulting
in the formation of
a
mixture of 4-methoxynitrosobenzene (2, 68%) and
1
4
-methoxynitrobenzene (3), verified by H NMR and GC-MS analysis of the reaction mixture.
SCHEME 2. Nitrosation of 1 by ipso-substitution with nitrosonium tetrafluoroborate.
The occurrence of the nitrobenzene derivative can be explained by traces of oxygen as was
described by Kochi.22
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 4 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
In order to improve the yields and decreasing the nitroarene by-product we examined the
nitrosodesilylation reaction in more detail by modifying the reaction temperature, the reaction
time and the amount of NOBF . The results of these optimizations are summarized in Table 1.
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
TABLE 1. Optimization of nitrosodesilylation reaction of 1a to 2a.a
NOBF
4
ratio 2a : 3a : 1a
by-product)
Temp.
entry
solvent
(equiv.)
(
1
2
3
4
5
6
7
8
9
CH
(CH
2
Cl
2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.2
2.0
1.5
1.3
1.3
1.3
1.1
1.0
20 °C
20 °C
42 : 7 : 0 (51)
41 : 8 : 36 (15)
0 : 0 : 3 (97)
66 : 10 : 10 (14)
87 : 13 : 0 (0)
10 : 0 : 90 (0)
93 : 7 : 0 (0)
93 : 2 : 0 (5)
95 :5 : 0 (0)
2
Cl)
2
EtOAc
THF
20 °C
20 °C
CH
3
CN
OH (5:1)
20 °C
20 °C
CH
3
CN/CH
3
CH
CH
CH
CH
3
3
3
3
CN
CN
CN
CN
20 °C
–40 °C
–40 °C
–40 °C
–40 °C
–40 °C
–40 °C
–40 °C
–40 °C
1
0
95 : 2 : 0 (3)
98 : 2 : 0 (0)
87 : 4 : 2 (7)
97 : 1 : 2 (0)
97 : 1 : 2 (0)
92 : 1 : 7 (0)
1
1
CH
3
CN
CN
CN
CN
CN
1
2b
3c
CH
CH
CH
CH
3
1
3
3
3
14
1
5
a
Reaction conditions: all reactions were performed on a 0.50 mmol scale and the reaction time was 30
1
b
C
minutes. The ratio of the products was determined by H NMR analysis. 0.05 M instead of 0.03 M.
0.1 M instead of 0.03 M.
ACS Paragon Plus Environment

Page 5 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
The use of CH
2
Cl2, which is the preferred solvent for the cobalt-catalyzed Diels-Alder
1
7
reaction, led to a mixture of the nitrosoarene 2, the nitroarene 3 and another uncharacterized
by-product (entry 1). Switching to a coordinating solvent, such as EtOAc or THF, the yield of
the nitrosoarene 2 was improved but the conversion of the starting material 1 was incomplete
(entry 3–4). Complete conversion could be achieved by using acetonitrile and the product could
be isolated in a good yield (87%) and only a minor quantity of the nitroarene (13%) was formed.
Furthermore, formation of the unknown by-product could be suppressed completely (entry 5).
Next, we attempted to increase the selective nitrosation by adding methanol in order to improve
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
3
the ability of the trimethylsilyl group acting as a leaving group. However, the reaction was
strongly inhibited by this additive (entry 6). Thus, acetonitrile proved to be the solvent of choice
for this transformation. In a second step, we optimized the temperature and the applied NOBF
4
equivalents. The outcome of the reaction was quite sensitive towards those parameters and the
yield could be significantly improved by lowering the temperature and simultaneously
decreasing the amount of the electrophile. The best yield was obtained at –40 °C using 1.3
equiv. of NOBF (entry 11). With those optimized conditions for the nitrosodesilylation reaction
4
in hand, we investigated a small number of other trimethylsilyl-substituted benzene derivatives
of type 1 to evaluate the scope of the reaction (Scheme 3).
SCHEME 3. Application of the reaction conditions to other starting materials.
a
Still remaining 10% of starting material 1d. The product also
contains 5% of 1-fluoro-4-nitrobenzene 3d. The ratio was
1
determined by H NMR analysis.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Using the optimized conditions, product 2a could be isolated in a very good yield of 91%. While
the yield for the derivative 2b was still acceptable (59%), rather disappointing results were
obtained for the electron-rich 2-methoxy-substituted derivative 2c. Accordingly, the reaction
conditions proved to be unsuitable for ortho-substituted arenes. This finding was supported by
1H NMR analysis of the crude product for the synthesis of 2c which indicated that the reaction
generated a number of undesired by-products. Also, this substrate gave no complete conversion,
likely because of its steric hindrance. Therefore, we conducted a second optimization using
(2-methoxyphenyl)trimethylsilane 1c as starting material to identify the critical aspects for the
nitrosodesilylation reaction with this substrate. The results for the nitrosodesilylation reaction
of 1c to 2c are summarized in Table 2.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
TABLE 2. Optimization of the nitrosodesilylation reaction of 1c to 2c.a
ratio 1c : 2c : by-product
yield in %)
NOBF
4
entry
temperature
time
(
(equiv.)
1
2
1.3
.0
20 °C
–40 °C
30 °C
2 h
50 : 26 : 24 (nd)
0 : 85 : 15 (52%)
0 : 71 : 29 (nd)
2
10 min
10 min
2.0
3
4
5
2.0
20 °C
10 min
0 : 90 : 10 (58%)
2.0
20 °C
5 min
0 : 96 : 4 (50%)
a
Reaction conditions: all reactions were performed on a 0.50 mmol scale. The ratio of the products was
1
b
determined by H NMR analysis. Acetonitrile/methanol = 10:1.
To avoid incomplete conversion, the temperature was raised again to ambient temperature.
Nevertheless, conversion of the starting material utilizing 1.3 equivalents NOBF was still
4
incomplete after 2 hours reaction time (entry 1). Increasing the amount of nitrosonium ions and
ACS Paragon Plus Environment

Page 7 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
increasing the reaction temperature to 30 °C gave complete conversion, but at the same time,
the amount of the undesired by-products also increased (entries 2–4). The best conditions were
found to be 5 minutes reaction time and 2.0 equivalents of NOBF
giving the highest product:by-product ratio of 96:4 and full conversion of the starting material
entry 5). On the other hand, the moderate yield of 52% can be attributed to purification issues
4
at ambient temperature
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
as the product is not trivial to isolate by column chromatography. Nevertheless, a number of
substrates were tested again in the nitrosodesilylation reaction with the optimized reaction
conditions for less reactive substrates and the results are summarized in Scheme 4.
SCHEME 4. Scope of the nitrosodesilylation reaction.
a
1
The yield was determined by H NMR analysis using
b
CH
2
Br
2
as internal standard.
The ratio of
nitrosoarene/protodesilylation by-product is 81:19 and
1
was determined by H NMR analysis.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Various electron-rich trimethylsilyl-substituted substrates were suitable for the explored
reaction. The best yield could be achieved with methyl- and methoxy-substituted derivatives
(52–68% yield).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Benzo[d][1,3]dioxol-5-yltrimethylsilane 1k afforded the corresponding nitrosoarene 2k in 73%
yield. In contrast, we discovered that the reaction of [1,1´-biphenyl]-4-yltrimethylsilane 1i to
afford product 2i led to the formation of significant quantities of the protodesilylated by-
product. Applying electron-deficient derivatives to the nitrosodesilylation reaction led to good
yields with the exception of the 4-cyano-substituted derivative 1l.
Mechanistically, the described nitrosodesilylation reaction proceeds via an electrophilic
+
19
aromatic substitution with NO acting as the electrophile. F NMR spectroscopy was used to
follow the course of the reaction subjecting (4-fluorophenyl)trimethylsilane (1d) to the reaction
conditions shown in Scheme 3. Monitoring the chemical shift of the aromatic fluorine atom, it
becomes apparent that the nitrosoarene 2d was not formed until the aqueous workup was
performed (see Figure S1–S8 in SI). This could be explained by the formation of nitroso-
substituted arenes which form a complex with additional NOBF
4
as described by Kochi.24,13a

29
Also, the additional high field signal at  F = –158.0 ppm reveals characteristic Si satellites,
which indicates the formation of Me
3
SiF as by-product. This assumption was confirmed by a
2
9

Si{H} INEPT NMR spectrum showing the chemical shift of  Si = 33.6 ppm and a
1
25
coupling constant of J(Si-F) = 272.6 Hz (see Figures S1–S6 in SI). These results suggest that
the trimethylsilyl group abstracted a fluoride anion from BF -
under formation of Me SiF and
BF . The proposed mechanism of the nitrosodesilylation is shown in Scheme 4.
4
3
3
ACS Paragon Plus Environment

Page 9 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
SCHEME 4. Proposed mechanism of the nitrosodesilylation.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Conclusion
In summary, we realized a new approach for the synthesis of nitrosoarenes by
nitrosodesilylation reaction for a number of different starting materials with good success. The
reaction conditions had to be adjusted to the electronic and steric conditions present in the
starting materials. Accordingly, the trimethylsilyl-substituted alkynes that we initially used in
our cobalt-catalyzed Diels-Alder reactions can be seen as synthon for a nitrosyl-substituted
1
9
alkyne. Finally, we were able to monitor the ipso-nitrosation reaction by F NMR analysis and
+
characterized the proposed intermediate 4 that is formed with additional NO ions. The
intermediate 4 was converted into the desired nitrosoarene derivatives during the aqueous work-
up.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
Experimental Section
General Information. All reactions with air or water sensitive starting materials were carried
out under argon atmosphere in heat-gun-dried glassware using Schlenk techniques. THF was
refluxed under nitrogen atmosphere and freshly distilled from sodium/benzophenone and stored
under nitrogen atmosphere. Dichloromethane and acetonitrile were stored over molecular
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
sieves under nitrogen atmosphere. Co(dppp)Br
2
was prepared following literature procedures.26
ZnI was dried in vacuo at 220 °C and stored in a Schlenk tube under argon atmosphere.
2
Commercially available materials were used without further purification. The trimethylsilyl-
substituted arenes 1b, 1c, 1e, 1g, 1k and 1l were prepared with n-BuLi and 1a and 1d by using
Grignard reagents according to a literature known procedure.16
For thin layer chromatography Merck TLC plates (Silica 60, F254 with fluorescence indicator)
were used. Column chromatography was carried out on Macherey-Nagel silica gel 60 (230–
1
13
1
4
00 mesh). H and C{ H} NMR spectra were either recorded on a Bruker AV II 300 or AV
1
13
1
1
III HD 300 ( H NMR: 300 MHz, C{ H} NMR: 75 MHz) or AV III 500 ( H NMR: 500 MHz,
1
3
C{ H} NMR: 125 MHz, 19F NMR: 470 MHz, Si{ H} INEPT NMR: 99 MHz). The
1
29
1
29Si{H} INEPT NMR spectra were recorded with delay times D3 = 0.0068 s and
D4 = 0.0313 s. Chemical shifts are reported in parts per million (ppm) and are referenced to the
1
13
1
solvent peak of CDCl
CD
3
( = 7.26 ppm for H NMR and  = 77.16 ppm for C{ H} NMR) or
CN ( = 1.94 ppm for 1H NMR) as internal standard.
C
F
6
( F =

3
6
–
164.9 ppm) was used as internal standard for 19F NMR analysis. GC-MS spectra were
measured on an Agilent 6890 GC-system including a Hewlett-Packard 5973 Mass Selective
Detector. For EI-HRMS a Joel AccuTof GCv spectrometer with an energy of 70 eV and for
ESI-HRMS a LTQ-FT Ultra mass spectrometer (Thermo Fischer Scientific) was used. IR
spectra were recorded on a Bruker IFS 88 (FTIR) spectrometer.
General Procedure for the synthesis of trimethylsilyl-substituted arenes by using cobalt-
catalyzed Diels-Alder reaction.17b
Under argon atmosphere Co(dppp)Br
2
(0.20 mmol or 0.50 mmol, 10 mol%), zinc powder
(0.40 mmol or 1.00 mmol, 20 mol%) and anhydrous zinc iodide (0.40 mmol or 1.00 mmol,
2
0 mol%) were suspended in anhydrous dichloromethane (2.0 ml or 5.0 mL, 1.0 M), and the
ACS Paragon Plus Environment

Page 11 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
mixture was stirred for 10 minutes at ambient temperature. Then 2,3-dimethyl-1,3-butadiene
(2.20 mmol or 5.50 mmol, 1.1 equiv.) and the trimethylsilyl-substituted alkyne (2.00 mmol or
5.00 mmol, 1.0 equiv.) were added and the reaction mixture was stirred at ambient temperature.
After complete conversion of the alkyne (monitored by GC-MS analysis) the reaction mixture
was filtered through a small plug of silica gel and the solvent was removed under reduced
pressure. Without further purification the obtained product was dissolved in dichloromethane
(0.2 M) and cooled to 0 °C. In three portions 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
(2.60 mmol or 6.50 mmol, 1.3 equiv.) was added and the mixture was stirred at ambient
temperature for 30 minutes. Then the reaction mixture was filtered through a small plug of
deactivated silica gel (n-pentane) and the solvent was removed under reduced pressure yielding
the pure trimethylsilyl-substituted arene.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Trimethyl(2,4,5-trimethylphenyl)silane (1e): colorless oil; 82% (331 mg, 1.75 mmol);
1
eluent: n-pentane; H NMR (300 MHz, CDCl
3
, ppm):  = 7.22 (s, 1H), 6.97 (s, 1H), 2.41 (s,
1
3
1
3
1
1
H), 2.24 (s, 6H), 0.32 (s, 9H); C{ H} NMR (75 MHz, CDCl
3
, ppm):  = 141.1, 137.7, 135.9,
+
35.4, 132.9, 131.6, 22.5, 19.6, 19.3, 0.1; MS (EI) m/z (%) 192 (19, [M ]), 177 (100), 161 (8),
49 (9), 133 (8), 119 (5), 105 (8), 91 (8), 73 (8); HRMS (EI, m/z) calcd for C12H20Si: 192.1334,
–
1
found 192.1316; IR (film, cm ) 2997, 2956, 1604, 1449, 1248, 1164, 1015, 978, 832, 754, 687,
39, 470, 442.
6
(3,4-Dimethylphenyl)trimethylsilane (1i): pale yellow oil; 84% (750 mg, 4.22 mmol); eluent:
1
n-pentane; H NMR (300 MHz, CDCl
3
, ppm):  = 7.27 (d, J = 8.5 Hz, 2H), 7.14 (d, J = 7.3 Hz,
1
3
1
1
H), 2.28 (s, 3H), 2.27 (s, 3H), 0.25 (s, 9H); C{ H} NMR (75 MHz, CDCl
3
, ppm):  = 137.6,
1
37.5, 136.0, 134.8, 131.1, 129.3, 19.9 (2C), –0.9. The analytic data are in accordance with the
literature.27
Preparation of (1,1´-biphenyl)-4-yltrimethylsilane (1h). According to a procedure of Hilt,28
under argon atmosphere phenylboronic acid (730 mg, 6.00 mmol, 1.2 equiv.),
(
4-bromophenyl)-trimethylsilane 1f (1.14 g, 5.00 mmol, 1.0 equiv.), K
30.0 mmol, 6.0 equiv.) and Pd(PPh (170 mg, 0.15 mmol, 3 mol%) were dissolved in a
mixture of degassed THF and water (10:1, 55 mL, 0.09 M). The reaction mixture was heated to
0 °C and stirred overnight. After complete conversion of the aryl bromide (monitored by GC-
3
PO
4
·6 H
2
O (6.91 g,
)
3 4
6
MS analysis) the mixture was filtered through a small plug of silica gel (n-pentane). The solvent
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 12 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
was removed under reduced pressure. The product was obtained in 85% yield (970 mg,
1
4.30 mmol) as red oil. H NMR (300 MHz, CDCl
3
, ppm):  = 7.62–7.60 (m, 6H), 7.47–7.42
, ppm):  = 141.8,
41.3, 139.4, 133.9, 128.9, 127.5, 127.3, 126.6, –0.9. The analytic data are in accordance with
1
3
1
(m, 2H), 7.38–7.33 (m, 1H), 0.31 (s, 9H); C{ H} NMR (75 MHz, CDCl
3
1
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
the literature.29
General Procedure for nitrosodesilylation reaction.
A) A round bottom flask was charged with acetonitrile (8.3 mL or 16.7 mL, 0.03 M), and
trimethylsilyl-substituted arene (0.25 mmol or 0.50 mmol, 1.0 equiv.) and cooled to –40 °C.
After adding NOBF
0 min. Then, the mixture was poured into 1:1-mixture of water/dichloromethane. The phases
were separated, the aqueous layer was extracted with dichloromethane and the combined
organic layers were dried (MgSO ), filtered, and concentrated under reduced pressure. If
necessary the crude product was purified by column chromatography or by filtering through a
4
(0.33 mmol or 0.65 mmol, 1.3 equiv.) the reaction mixture was stirred for
3
4
small plug of silica gel. The yield was either determined gravimetrically or by adding CH
2
Br
2
1
as internal standard for H NMR analysis.
B) A round bottom flask was charged with acetonitrile (8.3 mL or 16.7 mL, 0.03 M), and
trimethylsilyl-substituted arene (0.25 mmol or 0.50 mmol, 1.0 equiv.) and NOBF (0.50 mmol
4
or 1.00 mmol, 2.0 equiv.) were added. After stirring at ambient temperature for 30 min the
reaction mixture was poured into 1:1-mixture of water/dichloromethane. The phases were
separated, the aqueous layer was extracted with dichloromethane and the combined organic
layers were dried (MgSO
4
), filtered, and concentrated under reduced pressure. If necessary the
crude product was purified by column chromatography or by filtering through a small plug of
silica gel. The yield was either determined gravimetrically or by adding CH
2
Br as internal
2
1
standard for H NMR analysis.
1
-Methoxy-4-nitrosobenzene (2a): (4-Methoxyphenyl)trimethylsilane (90.2 mg, 0.50 mmol,
.0 equiv.) and NOBF (75.9 mg, 0.65 mmol, 1.3 equiv.) were reacted according to procedure
1
4
A. The crude product was purified by column chromatography on silica gel (n-pentane/diethyl
1
ether = 25:1) to afford 91% yield (62.3 mg, 0.45 mmol) of 2a as green solid. H NMR
(
300 MHz, CDCl , ppm):  = 7.91 (d, J = 8.5 Hz, 2H), 7.07–6.97 (m, 2H), 3.94 (s, 3H);
3
13
1
C{ H} NMR (75 MHz, CDCl
3
, ppm):  = 165.8, 164.2, 124.6, 114.0, 56.1; HRMS (EI) m/z
ACS Paragon Plus Environment

Page 13 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
+
calcd for C
the literature.14,30
7
H
7
NO ([M ]): 137.0477, found: 137.0487. The analytic data are in accordance with
2
1
,2-Dimethoxy-4-nitrosobenzene (2b): (3,4-Dimethoxyphenyl)trimethylsilane (105 mg,
0
.50 mmol, 1.0 equiv.) and NOBF (75.9 mg, 0.65 mmol, 1.3 equiv.) were reacted according to
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
procedure A. The crude product was purified by column chromatography on silica gel
(n-pentane/diethyl ether = 25:1 → 5:1) to afford 59% yield (49.5 mg, 0.27 mmol) of 2b as
1
green oil. H NMR (300 MHz, CDCl
3
, ppm):  = 8.49 (dd, J = 8.5, 2.2 Hz, 1H), 7.14 (d,
13
1
J = 8.5 Hz, 1H), 6.54 (d, J = 2.2 Hz, 1H), 4.02 (s, 3H), 3.86 (s, 3H); C{ H} NMR (75 MHz,
CDCl , ppm):  = 163.6, 156.1, 149.8, 128.7, 110.1, 94.5, 56.6, 56.6. The analytic data are in
accordance with the literature.11b
3
1
-Methoxy-2-nitrosobenzene (2c):
(2-Methoxyphenyl)trimethylsilane
1c
(45.1 mg,
0
.25 mmol, 1.0 equiv.) and NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to
4
procedure B. The crude product was purified by column chromatography on silica gel
(n-pentane/ethyl acetate = 10:1) to afford 52% yield (49.5 mg, 0.27 mmol) of 2c as brown oil.
1H NMR (300 MHz, CDCl
, ppm):  = 7.67 (ddd, J = 8.7, 7.1, 1.7 Hz, 1H), 7.35 (d, J = 8.5 Hz,
3
13
1
1
H), 6.84 (ddd, J = 8.1, 7.1, 1.1 Hz, 1H), 6.29 (dd, J = 8.1, 1.7 Hz, 1H), 4.27 (s, 3H); C{ H}
NMR (75 MHz, CDCl , ppm):  = 161.9, 158.2, 138.5, 119.5, 114.7, 108.6, 56.9. The analytic
3
data are in accordance with the literature.11b
1-Fluoro-4-nitrosobenzene (2d): (4-Fluorophenyl)trimethylsilane 1d (126.2.1 mg,
0.75 mmol, 1.0 equiv.) and NOBF (113.3 mg, 0.98 mmol, 1.3 equiv.) were reacted according
4
to procedure A. Without further purification the product 2d was obtained in 79% yield
1
(74.0 mg, 0.59 mmol) as brown oil. H NMR (300 MHz, CDCl
3
, ppm):  = 8.00–7.88 (m, 2H),
7.32–7.23 (m, 2H); 13C{ H} NMR (75 MHz, CDCl
1
, ppm):  = 163.8 (d, J = , 124.1 (d,
3
J = 9.6 Hz), 116.5 (d, J = 23.1 Hz). The fluoro-substitued carbon signal could not be resolved.
The analytic data are in accordance with the literature.31
1
-Methoxy-3-nitrosobenzene (2e):
0.25 mmol, 1.0 equiv.) and NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to
procedure B. The crude product was purified by filtration through a small plug of silica gel
n-pentane/ethyl acetate = 10:1) to afford 57% yield (25.7 mg, 0.14 mmol) of 2e as brown oil.
1H NMR (300 MHz, CDCl
, ppm):  = 8.03 (dt, J = 7.5, 1.3 Hz, 1H), 7.61 (dd, J = 8.5, 7.4 Hz,
(3-Methoxyphenyl)trimethylsilane
1e
(45.1 mg,
4
(
3
1
3
1
1H), 7.29 (ddd, J = 8.4, 2.7, 1.0 Hz, 1H), 6.91 (dd, J = 2.7, 1.7 Hz, 1H), 3.87 (s, 3H); C{ H}
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
NMR (75 MHz, CDCl
3
, ppm):  = 167.0, 160.6, 130.5, 122.9, 119.6, 100.0, 55.8. The analytic
data are in accordance with the literature.30
1
,2,4-Trimethyl-5-nitrosobenzene (2f): Trimethyl(2,4,5-trimethylphenyl)silane 1f (37.3 mg,
.25 mmol, 1.0 equiv.) and NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to
0
4
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
procedure B. Then CH
2
Br
2
was added to the crude product to determine the yield of 56%.
1H NMR (300 MHz, CDCl
, ppm):  = 7.27 (s, 1H), 6.15 (s, 1H), 3.23 (s, 3H), 2.28 (s, 3H),
3
1
3
1
2.20 (s, 3H); C{ H} NMR (75 MHz, CDCl
3
, ppm):  = 165.2, 147.0, 140.3, 134.3, 133.7,
08.8, 20.5, 19.0, 16.8. The analytic data are in accordance with the literature.13a
-Bromo-4-nitrosobenzene (2g): (4-Bromophenyl)trimethylsilane 1g (57.3 mg, 0.25 mmol,
(58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to procedure
B. The crude product was purified by filtration through a small plug of silica gel
1
1
1.0 equiv.) and NOBF
4
(n-pentane/ethyl acetate = 10:1) to afford 71% yield (32.8 mg, 0.18 mmol) of 2g as green oil.
1H NMR (300 MHz, CDCl
, ppm):  = 7.78 (s, 4H); C{ H} NMR (75 MHz, CDCl , ppm):
13
1
3
3

= 164.0, 132.9, 131.8, 122.3. The analytic data are in accordance with the literature.11b
1-Methyl-4-nitrosobenzene (2h): (4-Methylphenyl)trimethylsilane 1h (41.1 mg, 0.25 mmol,
1
.0 equiv.) and NOBF
B. Then CH Br
300 MHz, CDCl
4
(58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to procedure
1
2
2
was added to the crude product to determine the yield of 68%. H NMR
(
3
, ppm):  = 7.80 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 2.44 (s, 3H);
1
3
1
C{ H} NMR (75 MHz, CDCl , ppm):  = 165.7, 147.3, 129.9, 121.4, 22.1. The analytic data
3
are in accordance with the literature.11b, 33
4
-Nitroso-1,1´-biphenyl (2i): (1,1´-Biphenyl)-4-yltrimethylsilane 1i (56.6 mg, 0.25 mmol,
.0 equiv.) and NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to procedure
Br was added to the crude product to determine the yield of 81%. The mixture
contained 15% of protodesilylation by-product. The product was obtained as orange solid.
1H NMR (300 MHz, CDCl
, ppm):  = 7.98 (d, J = 8.7 Hz, 2H), 7.83 (d, J = 8.7, 2H), 7.70–
1
4
B. Then CH
2
2
3
2
3
13
1
7
.64 (m, 2H), 7.55–7.42 (m, 3H); C{ H} NMR (75 MHz, CDCl
3
, ppm):  = 165.1, 148.2,
1
39.3, 129.3, 129.1, 128.0, 127.6, 121.8. The analytic data are in accordance with the
literature.14
1
,2-Dimethyl-4-nitrosobenzene (2j): (3,4-Dimethylphenyl)trimethylsilane 1j (44.6 mg,
.25 mmol, 1.0 equiv.), NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to
Br
1H NMR (300 MHz, CDCl
0
4
procedure B. Then CH
2
2
was added to the crude product to determine the yield of 59%.
3
, ppm):  = 7.71 (dd, J = 8.0, 2.0 Hz, 1H), 7.60 (s, 1H), 7.35 (d,
1
3
1
J = 8.0 Hz, 1H), 2.39 (s, 3H), 2.34 (s, 3H); C{ H} NMR (75 MHz, CDCl , ppm):  = 166.3,
3
ACS Paragon Plus Environment

Page 15 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
1
46.1, 137.8, 130.4, 121.8, 119.7, 20.5, 18.9. The analytic data are in accordance with the
literature.33
5
-Nitrosobenzo[d][1,3]dioxole (2k): Benzo[d][1,3]dioxol-5-yltrimethylsilane 1k (48.6 mg,
.25 mmol, 1.0 equiv.) and NOBF (58.4 mg, 0.50 mmol, 2.0 equiv.) were reacted according to
0
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
procedure B. The crude product was purified by column chromatography on silica gel
(n-pentane/ethyl acetate = 10:1) to afford 73% yield (27.5 mg, 0.18 mmol) of 2k as green solid.
1H NMR (300 MHz, CDCl
, ppm):  = 8.59 (dd, J = 8.1, 1.9 Hz, 1H), 7.14 (d, J = 8.2 Hz,
3
1
3
1
1
1
H), 6.42 (d, J = 1.9 Hz, 1H), 6.10 (s, 2H); C{ H} NMR (75 MHz, CDCl , ppm):  = 165.0,
3
54.2, 149.4, 133.0, 108.3, 102.9, 91.8. The analytic data are in accordance with the literature.34
Supporting Information Available:
1
13
1
Analytical data and NMR spectra of isolated compounds; H and C{ H} NMR spectra for
selected compounds. This material is available free of charge via the internet at
http://pubs.acs.org
References
(
1) a) Streith, J.; Defoin, A. Synthesis 1994, 1107–1117; b) Vogt, P. F.; Miller, M. J.
Tetrahedron, 1998, 54, 1317–1348; c) Scholz, S.; Plietker, B. Org. Chem. Front. 2016, 3, 1295–
298; d) Kresze, G.; Schulz, G. Tetrahedron 1961, 12, 7–12; e) Frazier, C. P.; Bugarin, A.;
1
Engelking, J. R.; Read de Alaniz, J. Org. Lett. 2012, 14, 3620–3623; f) Stephenson, G. R.;
Balfe, A. M.; Hughes, D. L.; Kelsey R. D. Tetrahedron Lett. 2010, 51, 6806–6809.
(2) a) Ouyang, J.; Mi, X.; Wang, Y.; Hong, R. Synlett 2017, 28, 762–772; b) Adam, W.; Krebs,
O. Chem. Rev. 2003, 103, 4131–4146; c) Adam, W.; Bottke, N.; Engels, B.; Krebs, O. J. Am.
Chem. Soc. 2001, 123, 5542–5548; d) Adam, W.; Degen, H.-G.; Krebs, O.; Saha-Möller, C. R.
J. Am. Chem. Soc. 2002, 124, 12938–12939; e) Lu, X. Org. Lett. 2004, 6, 2813–2815.
(3) a) Momiyama, N.; Torii, H.; Saito, S.; Yamamoto, H. PNAS 2004, 101, 5374–5378; b)
Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 5360–5361; c) Ramakrishna, I.;
Bhajammanavar, V.; Mallik, S.; Baidya, M. Org. Lett. 2017, 19, 516–519; d) Ramakrishna, I.;
Sahoo, H.; Baidya, M. Chem. Commun. 2016, 52, 3215–3218.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 16 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
4) a) Bubnov, Y. N.; Pershin, D. G.; Karionova, A. L.; Gurskii, M. E. Mendeleev Commun.
2002, 12, 202–203; b) Kyne, R. E.; Ryan, M. C.; Kliman, L. T.; Morken, J. P. Org. Lett. 2010,
1
2, 3796–3799; c) Li, Y.; Chakrabarty, S.; Studer, A. Angew. Chem. Int. Ed. 2015, 54, 3587–
3
591.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
5) Kopp, F.; Sapountuis, I.; Knochel, P. Synlett 2003, 885–887.
(6) Asymmetric Diels-Alder reaction: a) Yamamoto, Y.; Yamamoto, H. Eur. J. Org. Chem.
006, 2031–2043; b) Waldmann, H.; Synthesis 1994, 535–551; c) Jana, C. K.; Grimme, S.;
2
Studer, A. Chem. Eur. J. 2009, 15, 9078–9084; d) Jana, C. K.; Grimme, S.; Studer, A. Chem.
Eur. J. 2008, 14, 6326–6328. Asymmetric nitroso-aldol reaction: e) Merino, P.; Tejero, T.;
Delsoa, I.; Matutec, R. Synthesis 2016, 48, 653–676; f) Yanagisawa, A.; Lin, Y.; Takeishi, A.;
Yoshida, K. Eur. J. Org. Chem. 2016, 5355–5359; g) Momiyama, N.; Yamamoto, H. J. Am.
Chem. Soc. 2004, 126, 5360–5361; h) Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc. 2005,
127, 1080–1081; i) Kawasaki, M.; Li, P.; Yamamoto, H. Angew. Chem. Int. Ed. 2008, 47, 3795–
3
797.
7) Catalytic and asymmetric Diels-Alder reaction: a) Dochnahl, M.; Fu, G. C. Angew. Chem.
Int. Ed. 2009, 48, 2391–2393; b) Jana, C. K.; Studer, A. Angew. Chem. Int. Ed. 2007, 34, 6542–
544; c) Yamamoto, Y.; Yamamoto, H. Angew. Chem. Int. Ed. 2005, 44, 7082–7085; d)
(
6
Yamamoto, Y.; Yamamoto, H. J. Am. Chem. Soc. 2004, 126, 4128–4129. Catalytic and
asymmetric nitroso-ene reaction: e) Frazier, C. P.; Engelking, J. R.; Read de Alaniz, J. J. Am.
Chem. Soc. 2011, 133, 10430–10433; f) Sandoval, D.; Samoshin, A. V.; Read de Alaniz, J. Org.
Lett. 2015, 17, 4514−4517; g) Murru, S.; Gallo, A. A.; Srivastava, R. S. J. Org. Chem. 2012,
7
7, 7119−7123. Catalytic and asymmetric nitroso-aldol reaction: h) Yanagisawa, A.; Fujinami,
T.; Oyokawa, Y.; Sugita, T.; Yoshida, K. Org. Lett. 2012, 14, 2434–2437.
(8) Gowenlock, B. G.; Richter-Addo, G. B. Chem. Rev. 2004, 104, 3315–3340.
(
9) a) Di Nunno, L.; Florio; S.; Todesco, P. E.; J. Chem. Soc. (C), 1970, 1433–1434; b) Yost,
Y.; Gutmann, H. R. J. Chem. Soc. (C), 1970, 2497–2499.
10) a) Priewisch, B.; Rück-Braun, K. J. Org. Chem. 2005, 331, 110–117; b) Tian, X.; Zhang,
C.; Xu, Q.; Li, Z.; Shao, X. Org. Biomol. Chem. 2017, 15, 3320–3323.
11) a) Defoin, A. Synthesis 2004, 706–710; b) Fountoulaki, S.; Gkizis, P. L.; Symeonidis, T.
S.; Kaminioti, E.; Karina, A.; Tamiolakis, I.; Armatas, G. S.; Lykakisa, I. N. Adv. Synth. Catal.
016, 358, 1500–1508; c) Zhu, Z.; Espenson, J. H. J. Org. Chem. 1996, 60, 1326–1332; d)
(
(
2
Zhao, D.; Johansson, M.; Bäckvall, J.-E. Eur. J. Org. Chem. 2007, 4431–4436; e) Trautwein,
G.; El Bakkali, B.; Alcañiz-Monge, J.; Artetxe, B.; Reinoso, S.; Gutiérrez-Zorrilla, J. M. J.
Catal. 2015, 331, 110–117.
ACS Paragon Plus Environment

Page 17 of 18
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(
12) Zyk, N. V.; Nesterov E. E.; Khiobystov A. N.; Zefirov, N. S. Russ. Chem. Bull. 1999, 48,
506–509.
13) a) Bosch, E.; Kochi, J. K. J. Org. Chem. 1994, 59, 5573–5586; first synthesis of nitroso
benzene: Baeyer, A. Chem. Ber. 1874, 7, 1638.
14) Molander, G. A.; Cavalcanti, L. N. J. Org. Chem. 2012, 77, 4402–4412.
(
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
(15) a) Snieckus, V.; Zhao, Z. Org. Lett. 2005, 7, 2523–2526; b) Birkofer, L.; Franz, M. Chem.
Ber. 1971, 104, 3062–3068.
(
16) a) Keay, B. A. Sci. Synth. 2002, 4, 685–712; Ball, L. T.; Green, M.; Lloyd-Jones, G. C.; b)
Russell, C. A. Org. Lett. 2010, 12, 4724–4727.
17) a) Hilt, G.; Janikowski, J.; Hess, W. Angew. Chem. Int. Ed. 2006, 45, 5204–5206; b) Hilt,
G.; Janikowski, J. Org. Lett. 2009, 11, 773–776.
18) Möckel, R.; Hilt, G. Org. Lett. 2015, 17, 1644–1647.
(
(
(19) Möckel, R.; Hille, J.; Winterling, E.; Weidemüller, S.; Faber, T. M.; Hilt, G. Angew. Chem.
Int. Ed. 2018, 57, 442–445.
(20) Gowenlock, B. G.; Maidment, M. J.; Orrell, K. G.; Prokeš, I.; Roberts, J. R. J. Chem. Soc.,
Perkin Trans. 2, 2001, 1904–1911.
(
(
(
21) Seel, F.; Meier, H. Angew. Chem. 1956, 68, 272–284.
22) Kim, E. K.; Kochi, J. K. J. Org. Chem. 1989, 54, 1692–1702.
23) Ball, L. T.; Lloyd-Jones, G. C.; Russell, C. A. J. Am. Chem. Soc. 2014, 136, 254–264.
(24) For a detailed discussion of the bonding situation in adduct 4, see: a) Lindeman, S. V.;
Bosch, E.; Kochi, J. K. J. Chem. Soc., Perkin Trans. 2, 2000, 1919–1923. See also: b) Kim, E.
K.; Kochi, J. K. J. Chem. Soc. 1991, 113, 4962–4974; c) Atherton, J. H.; Moodie, R. B.; Noble,
D. R. J. Chem. Soc., Perkin Trans. 2, 2000, 229–234; d) Brownstein, S.; Gabe, E.; Irish, B.;
Lee, F.; Louie, B.; Piotrowski, A. Can. J. Chem. 1987, 65, 445–450.
(
25) Lehmann, M.; Schulz, A.; Villinger, A. Angew. Chem. Int. Ed. 2009, 48, 7444–7447.
26) Hilt, G.; Lüers, S. Synthesis 2002, 609–618.
(
(27) Kim, H. U.; Park, O. Y.; Park, J. B.; Hwang, D.-H. J. Nanosci. Nanotechnol. 2016, 16,
0465–10469.
1
(28) Kuttner, J. R.; Hilt, G. Macromolecules 2014, 47, 5532–5541.
(29) Aufiero, M.; Scattolin, T.; Proutière, Schoenebeck, F. Organometallics 2015, 34, 5191–
5195.
30) Gowenlock, B. G.; Maidment, M. J.; Orrell, K. G.; Prokes, I.; Roberts, J. R. J. Chem. Soc.,
Perkin Trans. 2 2001, 1904–1911.
(
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 18 of 18
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
31) a) Fletcher, D. A.; Gowenlock, B. G.; Orrell, K. G. J. Chem. Soc., Perkin Trans 2 1997,
2201–2205; b) Al-Tahou, B. M.; Gowenlock, B. G. Recl. Trav. Chim. Pays-Bas 1986, 105,
53–355.
32) Arundhathi, R.; Damodara, D.; Mohan, K. V.; Lakshmi, K.; Likhar, P. R. Adv. Synth.
2
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Catal. 2013, 355, 751–756.
(33) Atherton, J. H.; Moodie, R. B.; Noble, D. R. J. Chem. Soc., Perkin Trans. 2 1999, 699–
7
05.
(34) Krohn, K.; Küpke, J.; Rieger, H. J. Prakt. Chem. 1997, 339, 335–339.
ACS Paragon Plus Environment