Redox reaction between benzyl azides and aryl azides: concerted synthesis of aryl nitriles and anilines

Article abstract of DOI:10.1039/c6ob02615j

A unique and novel reaction between benzyl azides and aryl azides is described to synthesize aryl nitriles and anilines concurrently, which is catalyzed with a photoactivated diruthenium complex. N-Unsubstituted imines (N-H imines) are generated first from benzyl azides, followed by the hydrogen transfer reaction between N-H imines and aryl azides. A wide range of aryl nitriles and anilines were synthesized under neutral and mild reaction conditions.

Full text of DOI:10.1039/c6ob02615j

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ISSN 1477-0520
COMMUNICATION
Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
benzene
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DOI: 10.1039/C6OB02615J
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ARTICLE
Redox reaction between benzyl azides and aryl azides: Concerted
synthesis of aryl nitriles and anilines
Yongjin Kim,a Young Ho Rheea* and Jaiwook Parka*
Received 00th January 20xx,
Accepted 00th January 20xx
A unique and novel reaction between benzyl azides and aryl azides is described to synthesize aryl nitriles and anilines
concurrently, which is catalyzed by a photoactivated diruthenium complex. N-Unsubstituted imines (N-H imines) are
generated first from benzyl azides, followed by the hydrogen transfer reaction between N-H imines and aryl azides. A wide
range of aryl nitriles and anilines were synthesized under neutral and mild reaction conditions.
DOI: 10.1039/x0xx00000x
www.rsc.org/
compounds.12 However, these methods are still suffer from
the use of stoichiometric or excess amount of oxidant or
Introduction
additives
Recently, we have reported the transformation of alkyl
azides into the corresponding N-H imines, in which
diruthenium complex acts as the catalyst under mild and
neutral conditions.13 In attempts to extend the utility of
.
Organic nitriles are important intermediates in organic
synthesis for versatile organic compounds such as amides,
ketones, amines and heterocyclic compounds1 and valuable
building blocks in natural products, pharmaceuticals,
agricultural chemicals, and functional materials.2
a
1
1
towards aryl azides, we observed unexpected formation of
benzonitrile in the reaction of benzyl azide in the presence of
phenyl azide (Scheme 1). Herein, we wish to report a unique
and novel redox reaction between benzyl azides and aryl
azides to afford a wide range of aryl nitriles and anilines: N-H
imines are generated from benzyl azides followed by the
dehydrogenation of N-H imines and hydrogenation of aryl
azides with the aid of ruthenium catalysis.
For these extensive applications, numerous methods for the
synthesis of nitriles are reported.3 Sandmeyer reaction4 and
the cyanation of aryl halides are classic methods for the
synthesis of organic nitriles.5 Although there are considerable
advances in the cyanation of aryl halides, these methods suffer
from the use of stoichiometric amount of toxic reagents and
the generation of large amount of inorganic waste. Alternative
methods are reported including the oxidation of benzyl
alcohols in the presence of ammonia6 and the dehydration of
aldoximes7 or primary amides.8 However, the oxidation
requires excess amount of ammonia and oxidants, while the
dehydration needs stoichiometric dehydrating reagents or
azeotropic conditions. Recently Jiao and co-workers reported
the synthesis of nitriles from methyl arenes or benzyl halides
with azide source and oxidants such as phenyliodonium
diacetate (PIDA) and 2,3-dichloro-5,6-dicyanobenzoquinone
(DDQ).9 In these transformations benzylic azides are suggested
as the intermediates. Although these transformations are
unique and novel, excess amount of strong oxidants are
required for the nitrile formation. Some other direct
transformations to nitriles from organic azides are also
reported such as tert-butyl hydroperoxide mediated oxidation
of azides,10 bromine trifluoride mediated transformation of
Scheme 1. Redox reaction between benzyl azide and phenyl azide.
Results and discussion
To optimize the reaction conditions, the reaction of 1-
(azidomethyl)-4-methoxybenzene 2a with methyl 4-
azidobenzoate 4a was tested under various conditions (Table
1). The transformation of 3a was not successful in the absence
of light (entry 1). Notably, the reaction of 3a with 4a was
completed at room temperature for 12 h in the presence of 30
W fluorescent light to afford 5a and 6a in quantitative yields
(entry 2). The use of 12 W blue LED as a light source was also
efficient for the transformation to give the products in
quantitative yields (entry 3). Interestingly, the reaction was
completed within 2 h at 70 oC to afford the products in
quantitative yields although the conversion was incomplete in
azides11 and oxidative C-C bond cleavage of
-azido carbonyl
a.Department of Chemistry, POSTECH (Pohang University of Science and
Technology), Pohang 790-784, Korea, E-mail: pjw@postech.ac.kr (homepage:
http://oml.postech.ac.kr)
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
o
2 h at 50 C (entries 4 and 5). As a solvent, acetonitrile was as
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good as THF, while toluene was a little less efficient (entries 6 nitrile. d The yield of aniline. e The conversions of 4b and 4c were
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DOI: 10.1039/C6OB02615J
and 7). One-pot one-step procedure was less efficient than the incomplete.
two-step procedure (entry 8). Products were formed in trace
amount without 30 W fluorescent light at 70 oC (entry 9).
Nine pairs of benzyl azides and aryl azides were reacted
under the conditions of entry 5 in Table 1 to investigate
electronic effects of para-substituents on the redox reaction
(Table 2). Generally, the redox reactions were successful to
give aryl nitriles and anilines in high yields, but incomplete
conversion of azides was observed in some of the reactions.
The redox reactions appeared to depend on the stability of N-
H imines and the efficiency of the transfer-hydrogenation
reaction between N-H imines and aryl azides. The incomplete
conversions of azides implicate that the hydrogenation of aryl
azides containing electron-donating group was less efficient
than that of the aryl azides containing electron-withdrawing
group to cause the side reactions of the relatively unstable N-H
imines generated from benzyl azides containing electron-
withdrawing group. However, it is noticeable that the electron-
poor benzyl azide 2c was converted to the corresponding aryl
nitrile almost quantitatively using the electron-poor aryl azide
Table 1. Reaction of 1-(azidomethyl)-4-methoxybenzene and
methyl 4-azidobenzoate under various conditions.a
Entry
Solvent
Temp. (oC) Time (h) Yields (5a/6a) (%)b
1
2c
3d
4
5
6
7
8e
9f
THF
THF
THF
THF
THF
25
25
35
50
70
70
70
70
70
12
12
12
2
2
2
2
12
12
20/22
97/99
97/99
55/55
99/99
90/92
98/99
84/89
6/8
4a
.
Toluene
Acetonitrile
THF
Table 2. Synthesis of various aryl nitriles.a
THF
a
Typical reaction conditions: A solution of benzyl azide 2a
(0.25 mmol) and the ruthenium catalyst (2.0 mol%) in a
1
solvent was illuminated with 30W fluorescent light. After the
formation of N-H imine, aryl azide 4a (0.25 mmol) was added
b
1
and illuminated by light source or heated. Determined by H
c
NMR using dibromomethane as an internal standard.
d
Reaction was carried out under 30W fluorescent light.
Reaction was carried out under 12 W blue LED. e Reaction was
carried out by one-pot one-step procedure with 30W
f
fluorescent light. Reaction was carried out by one-pot one-
step procedure without fluorescent light.
Table 2. Electronic effects on the redox reactions.a,b
99%c/99%d 99%/99%
99%/99%
a
99%/99% 86%/86%e
79%/78%e 78%/80%e
A solution of benzyl azide
2 (0.25 mmol) and the ruthenium
99%/99%
98%/99%
catalyst (2.0 mol%) in THF was illuminated with 30 W
fluorescent light. After the formation of N-H imines, aryl azides
4a (0.25 mmol) was added, and the reaction mixture was
stirred for 2 h at 70 oC The yields of aryl nitriles were
1
b
a A solution of benzyl azide
THF was illuminated with 30 W fluorescent light for 2 h to
2 (0.25 mmol) and 1 (2.0 mol%) in
1
determined by H NMR using dibromomethane as an internal
generate N-H imines. Then aryl azides
4
(0.25 mmol) was
standard due to their volatility, while others were determined
after isolation. c The reaction was carried out for 4 h. d The N-H
imine was generated using 4 mol% of 1 for 1 h.
o
added, and the reaction mixture was stirred for 2 h at 70 C.b
1
The yields of aryl nitriles and anilines were determined by H NMR
using dibromomethane as an internal standard. The yield of aryl
c
2 | J. Name., 2012, 00, 1-3
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With focusing on the synthesis of aryl nitriles, various reaction with aryl azide produces a ruthenium azide complex
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benzylic azides were employed in the redox reaction with
methyl 4-azidobenzoate (4a). In most cases, aryl nitriles were
(
(
B
), followed by the formation of a rutheDnOiuI:m10n.1i0tr3e9/nCe6OcoBm02p6l1e5xJ
C) with liberation of N2 , which is tautomerized to a ruthenium
obtained quantitatively. Electronic effect and steric effect amido complex (
were not significant on the formation of aryl nitriles. The redox ruthenium amido complex
reaction was compatible with various functional groups such and a ruthenium imido complex (
as methoxy, trifluoromethyl, cyano, chloro, bromo, ester, and produced through dehydrogenation with regenerating the
D
). Proton transfer from N-H imine to the
leads to the formation of aniline
), from which aryl nitrile is
D
E
vinyl group. It is noticeable that formyl group in 5p, which is ruthenium hydride
labile to oxidation and nucleophilic addition reactions, was
also survived. In addition, acid-labile TMS-protected phenolic
benzonitrile 5q was obtained in quantitative yield.
A.
Since both aryl nitrile and aniline are formed in the reaction,
we utilized our new finding to the reaction of nitrile and
aniline for one-pot synthesis of amidines. In the presence of
sodium hydride, amidine
7 was obtained in 92% from the in
situ generated nitrile and aniline (Scheme 2).
Scheme 4. Possible pathway for the formation of nitrile and aniline.
Conclusions
In summary, we found a novel and unique ruthenium
catalyzed redox reaction between benzyl azides and aryl azides
to produce aryl nitriles and anilines in concerted manner. As
far as we know, this is the first observation that aryl azides act
as a formal oxidant to transform benzyl azides into aryl nitriles.
On the basis of neutral and mild reaction conditions without
additives, the substrate scope was wide to give valuable aryl
nitriles in high yields, some of which are hard to be afforded by
previous synthetic methods.
Scheme 2. One-pot synthesis of amidine.
To obtain mechanistic insight on the redox reaction,
deuterated benzyl azide
8 was employed to figure out the
deuterium transfer from benzyl azide to aryl azide. As a result,
nitrile 5b was obtained in quantitative yield and the
deuterated aniline 10 was formed in 94% yield (Scheme 3a).
Meanwhile, we investigated the catalytic activity of ruthenium
hydride complex 12 for the redox reaction, which is active for
the generation of N-H imines from alkyl azides (Scheme 3b).13
Indeed, the redox reaction between 2a and 4a proceeded with
the catalytic amount of the ruthenium hydride 12 to give the
nitrile 5a and the aniline 6a in 90% and 92%, respectively.
Experimental section
Air-sensitive manipulations were carried out with standard
Schlenk techniques under argon atmosphere. Commercial
chemicals used without further purification. Flash column
chromatography was carried out on silica gel (230-400 mesh)
as the stationary phase. 1H and 13C NMR spectra were
recorded with Bruker AVANCE III 300MHZ FT-NMR
spectrometer and chemical shift are given in δ ppm. 1H NMR
spectra were referenced to tetramethylsilane (TMS, 0 ppm).
13C NMR spectra were referenced to CDCl3 (77.23 ppm) as an
internal standard. Infrared spectra were recorded on a
Shimadzu IR-470 spectrometer with NaCl pellet. Mass spectral
data were obtained from the Korea Basic Science Institute
(Daegu) on a Jeol JMS 700 high resolution mass spectrometer.
Ruthenium complex 114 and 1115 were synthesized according
to the literature procedure
General procedure for synthesis of aryl nitriles and anilines.
The ruthenium catalyst (2.0 mol%, 0.005 mmol, 4.9 mg) was
added to a flame-dried J-Young flask filled with argon. The dry
THF (1.0 mL) and benzyl azide (0.25 mmol) were added under
a stream of argon. The reaction mixture was stirred for 2 h at
.
Scheme 3. Mechanistic investigation.
Based on the results described above, a reaction pathway
for the redox reaction is proposed in Scheme 4.
coordinatively unsaturated ruthenium species
from the ruthenium hydride 12 by light or heating.13 Then the
1
A
A is formed
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room temperature with a household 30W fluorescent light. (m, 2H); 13C NMR (75 MHz, CDCl3) δ = 190.8, 138.9, 133.1,
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DOI: 10.1039/C6OB02615J
After the accumulation of N-H aldimine, aryl azide (1.0 equiv, 130.1, 117.9, 117.8.
0.25 mmol) was added then stirred at 70 oC for 2 h. After 4-(tert-butyldimethylsilyloxy)benzonitrile (5o)20 Yield: 99%;
completion of the reaction, solvent was removed under Colorless liquid; H NMR (300 MHz, CDCl3) δ = 7.56-7.51 (m,
reduced pressure. The residue was purified by column 2H), 6.91-6.87 (m, 2H), 0.98 (s, 9H), 0.23 (s, 6H); 13C NMR (75
1
chromatography on silica gel to afford corresponding nitrile MHz, CDCl3) δ = 159.9, 134.2, 121.0, 119.4, 104.8, 25.7, 18.4, -
and aniline.
4.2.
1
4-methoxybenzonitrile (5a)16 Yield: 98%; White solid; H NMR Synthesis of amidine 7
(300 MHz, CDCl3) δ = 7.61-7.58 (m, 2H), 6.98-6.94 (m, 2H), 3.86 The ruthenium catalyst
1
was added to a flame-dried J-Young
(s, 3H); 13C NMR (75 MHz, CDCl3) δ = 163.0, 134.2, 119.4, 114.9, flask filled with argon. The dry THF (1.0 mL) and 2a (0.25 mmol)
104.2, 55.7.
4-methylbenzonitrile (5b)17 Yield: 99%; 1H NMR (300 MHz, was stirred for 2 h at room temperature with a household 30W
CDCl3, in crude mixture with an internal standard (CH2Br2)) δ = fluorescent light. After the accumulation of 3a 4a (1.0 equiv,
were added under a stream of argon. The reaction mixture
,
7.55-7.52 (m, 2H), 7.28-7.25 (m, 2H), 2.41 (s, 3H).
0.25 mmol) was added then stirred at 70 oC for 2 h. The
4-(trifluoromethyl)benzonitrile (5c)17 Yield: 98%; White solid; reaction mixture was cooled to room temperature then NaH
1H NMR (300 MHz, CDCl3) δ = 7.82 (d, J = 8.3 Hz, 2H), 7.77 (d, J (1.5 equiv, 0.375 mmol) is added at 0 C and stirred at room
= 8.5 Hz, 2H); 13C NMR (75 MHz, CDCl3) δ = 135.0, 134.5, 132.9, temperature for 12h. After completion of the reaction, the
126.44, 126.40, 126.34, 126.29, 125.1, 121.4, 117.6, 116.3.
Terephthalonitrile (5d)17 Yield: 98%; White solid; H NMR (300 with diethyl ether (3 x 5 mL). The oragnic layer was washed
MHz, CDCl3) δ = 7.80 (s, 4H); 13C NMR (75 MHz, CDCl3) δ = with H2O (2 x 30 mL), brine (30 mL), dried over anhydrous
o
o
reaction mixture was quenched with water at 0 C, extracted
1
133.0, 117.2, 116.9.
sodium sulfate, concentrated under reduced pressure. The
2-methylbenzonitrile (5e)17 Yield: 99%; 1H NMR (300 MHz, residue was recrystallized at -20oC (n-hex:dichloromethane =
CDCl3, in crude mixture with an internal standard (CH2Br2)) δ = 2:1) to afford amidine 7.
7.60-7.57 (m, 1H), 7.50-7.44 (m, 1H), 7.32-7.23 (m, 2H), 2.54 (s, 4-methoxy-N-phenylbenzimidamide (7)21 Yield: 92%; White
1
3H).
solid; H NMR (300 MHz, CDCl3) δ = 7.78 (d, J = 8.5 Hz, 2H),
3-methylbenzonitrile (5f)17 Yield: 99%; 1H NMR (300 MHz, 7.33 (t, J = 7.7 Hz, 2H), 7.06-7.01 (m, 1H), 6.97-6.90 (m, 4H); 13
CDCl3, in crude mixture with an internal standard (CH2Br2)) δ = NMR (75 MHz, CDCl3) δ = 161.7, 154.9, 149.6, 129.6, 128.6,
C
7.46-7.31 (m, 4H), 2.38 (s, 3H).
123.1, 122.0, 113.9, 55.6.
Benzonitrile (5g) Yield: 90%; 1H NMR (300 MHz, THF-d8, in
crude mixture with an internal standard (CH3NO2)) δ = 7.71-
7.68 (m, 2H), 7.65-7.59 (m, 1H), 7.52-7.47 (m, 2H).
Synthesis of 1-(azidomethyl-d2)-4-methylbenzene 8
To a solution of methyl 4-methylbenzoate (5.0 mmol) in THF
(10 mL), lithium aluminum deteride (1.2 equiv, 6.0 mmol) was
added at 0 oC. The reaction mixture was stirred at room
temperature for 3 h. After completion of the reaction, the
mixture was quenched with 1 N HCl (10 mL), extracted with
ethyl acetate (3 x 10 mL). The oragnic layer was washed with
H2O (30 mL) and brine (30 mL), dried over anhydrous sodium
sulfate, concentrated under reduced pressure. The crude
residue was directly used for next step without further
purification. To a solution of p-tolylmethanol-d2 and diphenyl
phosphoryl azide (DPPA) (2.0 equiv, 10 mmol) in toluene (15
mL), Diazabicyclo[5.4.0]undec-7-ene (DBU) (2.0 equiv, 10
4-chlorobenzonitrile (5h)16 Yield: 99%; White solid; 1H NMR
(300 MHz, CDCl3) δ = 7.63-7.59 (m, 2H), 7.49-7.45 (m, 2H); 13C
NMR (75 MHz, CDCl3) δ = 139.7, 133.5, 129.8, 118.1, 110.9.
4-bromobenzonitrile (5i)18 Yield: 99%; White solid; 1H NMR
(300 MHz, CDCl3) δ = 7.66-7.62 (m, 2H), 7.55-7.51 (m, 2H); 13C
NMR (75 MHz, CDCl3) δ = 133.6, 132.8, 128.1, 118.2, 111.4.
4-tert-butylbenzonitrile (5j)16 Yield: 99%; Colorless liquid; 1H
NMR (300 MHz, CDCl3) δ = 7.60-7.57 (m, 2H), 7.50-7.46 (m, 2H),
1.33 (s, 9H); 13C NMR (75 MHz, CDCl3) δ = 156.8, 132.2, 126.4,
119.3, 109.5, 35.5, 31.1.
1
2-naphthonitrile (5k)16 Yield: 96%; White solid; H NMR (300
o
mmol) was added dropwise at 0 C. The reaction mixture was
MHz, CDCl3) δ = 8.22 (s, 1H), 7.92-7.87 (m, 3H), 7.67-7.57 (m,
3H); 13C NMR (75 MHz, CDCl3) δ = 134.8, 134.3, 132.4, 129.4,
129.2, 128.6, 128.2, 127.8, 126.5, 119.4, 109.6.
stirred at room temperature for 12 h and quenched with water
(30 mL). The solution was extracted with dichloromethane (3 x
20 mL). The organic was washed with H2O (2 x 30 mL) brine (30
mL), dried over anhydrous sodium sulfate, concentrated under
reduced pressure. The residue was purified by flash column
Methyl 4-cyanobenzoate (5l)16 Yield: 99%; White solid; 1H
NMR (300 MHz, CDCl3) δ = 8.16-8.13 (m, 2H), 7.76-7.74 (m, 2H),
3.97 (s, 3H); 13C NMR (75 MHz, CDCl3) δ = 165.6, 134.1, 132.4,
130.3, 118.2, 116.6, 52.9.
chromatography to afford the deuterated azide 8.
1-(azidomethyl-d2)-4-methylbenzene (8)
1
4-vinylbenzonitrile (5m)19 Yield: 96%; Colorless liquid; H NMR
Yield: 60% (2 steps); Pale yellow liquid; 1H NMR (300 MHz,
CDCl3) δ = 7.26-7.18 (m, 4H), 2.37 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ = 138.3, 132.3, 129.6, 128.4, 54.46, 54.29, 54.11,
53.94, 21.3; IR(NaCl): = 3026, 3001, 2924, 2868, 2495, 2106,
1907, 1615, 1516 cm-1; HRMS (EI): m/z calcd. for C8H7D2N3:
149.0922; found: 149.0921.
(300 MHz, CDCl3) δ = 7.61 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 8.2 Hz,
2H), 6.72 (dd, J = 17.6, 10.9 Hz, 1H), 5.87 (d, J = 17.6 Hz, 1H),
5.45 (d, J = 10.9 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ = 142.1,
135.6, 132.6, 126.9, 119.1, 117.9, 111.3.
4-formylbenzonitrile (5n)17 Yield: 90%; White solid; 1H NMR
(300 MHz, CDCl3) δ = 10.10 (s, 1H), 8.03-7.99 (m, 2H), 7.87-7.84
4 | J. Name., 2012, 00, 1-3
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Senanayake, Angew. Chem. Int. Ed., 2016, 55, 326-330; e) Q.
Synthesis of nitrile and methyl-4-amino-d2-benzoate
The ruthenium catalyst (2.0 mol%, 0.0025 mmol) was added
to a flame-dried NMR reaction J-young tube and filled with
argon. The THF-d8 (0.6 mL) and (0.125 mmol) were added
1
8
Wu, Y. Luo, A. Lei and J. You, J. Am. Chem. Soc., 2016, 138
,
under a stream of argon. The reaction mixture was stirred for 2
h at room temperature with a household 30W fluorescent light.
After the accumulation of N-H aldimine, 4a (1.0 equiv, 0.125
mmol) was added then stirred at 70 oC for 2 h.
Methyl 4-amino(d-2)benzoate (10)
1H NMR (300 MHz, THF-d8, in crude mixture) δ = 7.73-7.68 (m,
2H), 6.55-6.51 (m, 2H), 3.73 (3H).
2885-2888; f) J.-J. Ge, C.-Z. Yao, M.-M. Wang, H.-X. Zheng, Y.-
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4
5
Synthesis of nitrile and methyl-4-amino-d2-benzoate
The ruthenium catalyst
to a flame-dried NMR reaction J-young tube and filled with
argon. The THF (0.6 mL) and (0.125 mmol) were added under
1 (2.0 mol%, 0.0025 mmol) was added
8
a stream of argon. The reaction mixture was stirred for 2 h at
room temperature with a household 30W fluorescent light.
After the accumulation of N-H aldimine, aryl azide (1.0 equiv,
Howlader and P. S. Mukherjee, J. Am. Chem. Soc., 2016, 138
1709-1716.
,
o
0.125 mmol) was added then stirred at 70 C for 2 h. The yield
6
7
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of methyl 4-amino-d2-benzoate 10 was determined by
deuterium NMR using THF-d8 as an internal standard.
Methyl 4-amino(d-2)benzoate (10)
2D NMR (500 MHz, THF-d8, in crude mixture with an internal
standard (THF-d8)) δ = 5.16 (s, 2D).
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The reaction using Ru-H 12 as a catalyst
Chem., 2015, 80, 11624-11628.
To a solution of the ruthenium chloride 11 (0.02 mmol) in THF
(1.0 mL), tributyltin hydride (0.02 mmol) was added. The
reaction mixture was stirred for 3 h at room temperature with
a 12W blue LED to generate the ruthenium hydride 12 (The
generation of 12 was checked by 1H and 13C NMR using THF-d8
a) S. H. Yang and S. Chang, Org. Lett., 2001, 3, 4209-4211; b)
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,
2a (0.25 mmol)
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4181-4186.
o
and 4a (0.25 mmol) were added and stirred at 70 C for 16 h
under illumination with a household 30 W fluorescent light.
After completion of the reaction, solvent was removed under
reduced pressure. The yield of 5a and 6a was determined by
1H NMR using dibromomethane as an internal standard.
8
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Acknowledgements
This work is supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIP)
(2015R1A2A2A01008130).
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18 S. Chiba, L. Zhang, G. Y. Ang and B. W.-Q. Hui, Org. Lett.,
2010, 12, 2052-2055.
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