Regioselective functionalisation of dibenzothiophenes through gold-catalysed intermolecular alkyne oxyarylation

Article abstract of DOI:10.1039/c5ob01241d

A protocol has been developed for direct Csp³-Csp² bond formation at the 4- and 6-positions of dibenzothiophenes using a gold(i) catalyst with terminal alkynes and dibenzothiophene-S-oxides. The sulfoxide acts as a traceless directing group to avoid the need to prefunctionalise at carbon. The iterative use of this protocol is possible and has been employed in the preparation of novel macrocyclic structures. In addition, a cascade process shows how oxyarylations can be combined with other processes resulting in complex, highly efficient transformations.

Full text of DOI:10.1039/c5ob01241d

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DOI: 10.1039/C5OB01241D
Regioselective functionalisation of dibenzothiophenes through
gold-catalysed intermolecular alkyne oxyarylation†
Matthew J. Barrett,a Paul W. Daviesa* and Richard S. Graingera*
Received 00th January 20xx,
Accepted 00th January 20xx
A protocol has been developed for direct Csp3-Csp2 bond formation at the 4- and 6-positions of dibenzothiophenes using a
gold(I) catalyst with terminal alkynes and dibenzothiophene-S-oxides. The sulfoxide acts as a traceless directing group to
avoid the need to prefunctionalise at carbon. The iterative use of this protocol is possible and has been employed in the
preparation of novel macrocyclic structures. In addition, a cascade process shows how oxyarylations can be combined with
other processes resulting in complex, highly efficient transformations.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Introduction
Dibenzothiophenes
are
aromatic
sulfur-containing
heterocycles of broad utility. The optical, redox and conducting
properties of dibenzothiophenes and their corresponding S,S-
dioxides have led to applications in materials science.1 S-
Substituted dibenzothiophenes are used as precursors to
triphenylenes2 and as a platform for the transfer of reactive
species such as F3C+ (Umemoto’s reagent),3 atomic oxygen
(O(3P)),4 nitrenes5 and carbenes.6 Biological and medicinal
chemistry applications of dibenzothiophenes and their S-
oxides have also been reported.7
Scheme 1 Proposed regiospecific functionalisation of dibenzothiophenes using the S-
oxide as a traceless directing group.
This and subsequent17d,e studies established that such
processes are regiospecific by virtue of proceeding via a [3,3]-
Functionalised dibenzothiophenes are generally prepared
through one of two main approaches. Late stage formation of
the dibenzothiophene core has been achieved through
intramolecular C-S8 or C-C (biaryl)9 bond formation and
benzannulation of thiophenes or benzothiophenes.10
Alternatively, dibenzothiophene undergoes regioselective
bromination at the 2,8-positions11 or the 3,7-positions of the
corresponding S,S-dioxide.12 Substitution at the 4- and 6-
positions however requires stoichiometric metallation using
organolithium or organoaluminium reagents.13,14 Here we
report a catalysis-based approach for direct carbon-carbon
bond formation at the unfunctionalised 4- and 6-positions of
dibenzothiophenes under mild and functional group tolerant
conditions.
sigmatropic rearrangement of the vinyl gold carbenoid
formed on attack of the sulfoxide to the gold-alkyne complex
(Scheme 2,
).21
B
A→C
Our interests in aromatic S-oxide chemistry15 and π-acid
catalysis16 led us to investigate whether 4-substituted
dibenzothiophenes could be accessed in an expedient fashion
from dibenzothiophene S-oxides by a gold-catalysed alkyne
oxyarylation.17,18,19 This approach should be regiospecific,
installing a Csp3-Csp2 bond with transfer of the oxygen atom to
generate the synthetically versatile α-arylcarbonyl motif
(Scheme 1).20
Following the introduction of alkyne oxyarylation with
sulfoxides in gold-catalysed intramolecular cycloisomerisations
by the groups of Toste17a and Zhang17b, the viability of an
intermolecular process was shown by Ujaque, Asensio and co-
workers (Scheme 2).17c
Scheme 2. General schematic for gold-catalysed oxyarylation reaction of alkynes
with sulfoxides.
Despite sulfoxide-based alkyne oxyarylation offering
substantial potential for atom-economic, functional group
tolerant and direct intermolecular aryl C-H functionalisation
routes into challenging aromatic substitution patterns, they
have been rarely employed in synthesis. In large part this can
a.Haworth Building, School of Chemistry, University of Birmingham, Edgbaston,
Birmingham, B15 2TT, UK.
† Electronic Supplementary Information (ESI) available: [general experimental
procedures, additional example of iterative process and NMR spectra for new
compounds]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Journal Name
be assigned to the challenges of ensuring that the key and 14 vs. 11 and 1), which differ substantially from those
View Article Online
DOI: 10.1039/C5OB01241D
aromaticity-disrupting [3,3]-sigmatropic rearrangement (
is favoured over elimination of a sulfide nucleofuge (
competing inter- or intramolecular attack of a nucleophile are in keeping with higher temperature and electron-density at
).17,22,23 In addition, structural elaboration of the sulfoxide the gold centre being likely to increase the rate of elimination
must not prevent it from being sufficiently nucleophilic to of the sulfide nucleofuge (Scheme 2,
).26,27
intercept the alkyne-gold complex , yet not force further Little counterion effect was observed and similar results were
B→
C)
conditions previously reported for the intermolecular
B→D
), or oxyarylation reaction with sulfoxides.17c,d These observations
(B→E
B→D
A
reaction at
B
to afford the biscarbonyl
G
alongside two obtained with the single component catalyst system (Entries
10 and 11). Re-evaluating the solvent showed CH2Cl2 to be
poor and that excellent selectivity was ultimately obtained in
equivalents of sulfide.24,25
toluene
at
0

C
using
(2,4-di-tert-
BuC6H3O)3PAu(NCCH3)SbF6,16d,28 affording 3a in high yield
Results and discussion
(Entry 17).
The use of dibenzothiophene-S-oxide
The viability of selective elaboration of a dibenzothiophene
through an alkyne oxyarylation approach was investigated
1 with different terminal
alkynes 2b-k was then studied in the oxyarylation reaction:
Chloro, aryl, vinyl and phthalimide substituents were well-
tolerated as were the methyl and silyl-ethers, affording
products 3b-k in generally good yields (Table 2, Entries 2-7).29
The α-hydroxyketone oxyarylation product 3g was also formed
in high yield (Entry 8) despite the potential for oxetan-3-one
formation by intramolecular capture of the vinylgold
intermediate by the propargylic alcohol, as reported using
cationic gold(I) catalysts and pyridine-N-oxides.30 This protocol
proved to be robust: a very similar yield was obtained even
when the reaction was run open to the air and using non-dried
toluene with only 1 mol% catalyst loading on larger scale
(Entries 4 and 5).
using dibenzothiophene-S-oxide
the combination of Ph3PAuCl/AgSbF6 in superheated CH2Cl2
from Asensio’s work17c generated
mixture of
dibenzothiophenes 3a and in high yield with the desired
oxyarylation product 3a as the minor component (Table 1,
Entry 1).
1 and hex-1-yne 2a. Applying
a
4
An investigation of the reaction conditions was undertaken to
explore the factors favouring the rearrangement pathway over
those leading to S-O bond cleavage and formation of
4 (Table
1). The most significant factors identified in this study proved
to be the use of electron-deficient rather than electron-rich
ligands on gold (compare entries 7 and 10 vs. 4, 8 and 9) and
the use of lower reaction temperatures (compare entries 13
Table 1. Study of the reaction conditions for oxyarylation using dibenzothiophene-S-oxidea
Entry
Gold catalyst
Solvent
Time /
h
Temp /
ºC
Conc.
M
Yield 1 /
%
Yield 3a /
Yield 4 /
%
Ratio 3a:4
b
b
b
%
1b
2
3
4
5
6
7
8
Ph3PAuCl/AgSbF6
Ph3PAuCl/AgSbF6
Ph3PAuCl/AgSbF6
CH2Cl2
ClCH2CH2Cl
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH2Cl2
16
16
16
16
16
16
16
16
16
16
16
3
70
70
70
70
70
70
70
70
70
70
70
70
RT
RT
RT
RT
0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.1
0.1
0.1
0.1
0.1
0.1
0
10d
0
12
52
36
5
51
52
<5
<5
<5
8
<5
29
0
37
20
39
41
4
61
30d
36
31
22
24
24
24
24
17
16
20
10
14
5
1:1.6
-
c
c
c
1.1:1
1.3:1
1:5.5
1:6.0
1.8:1
1:2.4
1:3.0
2.8:1
3.0:1
2.2:1
6.7:1
3.9:1
3.4:1
10.5:1
11.4:1
Ph3PAuCl/AgOTsc
AuCl
AuPicolinateCl2
4
(p-F3CC6H4)3PAuCl/AgOTsc
XPhosAuCl/AgOTsc
JohnPhosAuCl/AgOTsc
(ArO)3PAuCl/AgOTsc
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
(ArO)3PAu(NCCH3)SbF6
42
10
8
9
10
11
12
13
14
15
16
17
47
48
44
67
54
17
84
91
3
3
3
3
CH3CN
Toluene
Toluene
8
8
3
0
a 1 (0.10 mmol), 2a (0.20 mmol). b Yields calculated by 1H-NMR spectroscopy against a known quantity of internal standard (1,2,4,5-tetramethylbenzene). c Catalyst
prepared by in situ combination of equimolar quantity of the (Ligand)AuCl with the appropriate Ag(counterion) salt d Due to overlap with unidentified resonances
estimated yields were determined. XPhos = 2-Dicyclohexylphosphino-2,4,6-triisopropylbiphenyl; JohnPhos = (2-Biphenyl)di-tert-butylphosphine; Ar = (2,4-Di-tert-
butylphenyl).
2 | J. Name., 2012, 00, 1-3
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4).31 Under those conditions
effective than the unsubstituted pyridine-N-oxide and
1
proved to be as, or more-,
View Article Online
DOI: 10.1039/C5OB01241D
Table 2 Selective formation of C-4 substituted dibenzothiophenes using different
alkynes
substantially more effective than the diphenylsulfoxide in both
the oxidative formation of α,β-unsaturated imide
8 and α-
oxoimide 10. Hence may be considered as an alternative
1
reagent to diphenylsulfoxide in gold-catalysed oxidative
processes.32,33
Entry
R
Cond.
Mmol
Cat.
/mol%
Time
/h
Yield
/%a
1
2
3
4
5
6
7
8
9
10
11
12
13
nBu
(CH2)3Cl
A
A
A
A
A
A
A
A
A
B
B
B
B
0.2
0.2
0.2
0.2
2.0
0.5
2.0
0.2
0.1
0.3
0.2
0.2
0.2
5
5
5
5
1
1
5
5
5
5
5
5
5
0.75
0.75
0.75
0.75
2
87 3a
79 3b
65 3c
87 3d
84 3d
82 3e
52 3f
76 3g
48c3h
58 3h
40 3i
42 3j
62 3k
(CH2)2Ph
CH2OMe
CH2OMe
(CH2)4OTBDPS
CH2NPhth
CH(OH)nC7H15
Ph
2
20b
20b
1.5
20
Ph
2-BrC6H4
4-MeOC6H4
2-thienyl
20
20
20
Scheme 4 Comparison of reactivity in oxidative transformation of ynamides.§
a Yields of isolated material after flash chromatography. b Reactions stirred for 4 h
at 0 oC then warmed to rt over 16 hours. c Yield calculated by 1H-NMR
spectroscopy against a known quantity of internal standard (1,2,4,5-
tetramethylbenzene).
Toste and co-workers had previously reported that the gold-
catalysed reaction of 1,6-enynes in the presence of excess
diphenylsulfoxide led to the formation of aldehydes by
intramolecular cyclisation and capture of the intermediate
cyclopropyl gold carbene with sulfoxide.24a Given the higher
The use of phenyl acetylene gave lower yields and led to
reactivity observed of
(Scheme 4), the reaction of enyne substrates 11 was studied to
see whether would be sufficiently nucleophilic to allow the
1 compared to diphenylsulfoxide
formation of significant quantities of dibenzothiophene
4
under the standard conditions (Table 2, Entry 9). Further
reducing the temperature, which in-turn necessitated a higher
1
intermolecular reaction of the sulfoxide at the gold-alkyne
complex to compete with intramolecular cycloisomerisation.
Under our standard conditions the 1,6-enynes 11a and 11c
reacted cleanly to give the oxyarylation products 12a/c in high
yield (Scheme 5). In contrast, the cinnamyl derivative 11b and
dilution to maintain solubility of 1, gave improved yields which
were also seen with other aryl alkynes, including thiophene
and o-bromobenzene (Entries 10-13).
The 2,8-dibromo substitution pattern, which is useful for
further transformations in materials science applications,1 was
the malonate-derived enyne 11d led to the aldehydes 13b
with low conversion. On this basis, the relatively high efficacy
of dibenzothiophene S-oxide as a nucleophile towards gold
/d
readily accommodated with S-oxide
5 reacting to afford the
oxyarylation product in good yield (Scheme 3).
6
1
alkyne complexes allows it to compete with an intramolecular
enyne cycloisomerisation so long as the latter pathway is not
strongly biased toward cyclisation by reactive rotamer effects
or use of more electron-rich alkenes. Products arising from
capture of the vinyl gold carbenoid by the tethered alkene
were not observed.34
Iterative application of the oxyarylation reaction was then
tested to selectively functionalise both the 4- and 6-positions
of dibenzothiophene (Scheme 5). The gold-catalysed reactions
of 14, from selective oxidation of 12a using mCPBA,35 with 1,6-
and 1,7-enynes 11a and 15 afforded high yields of the 4,6-
disubstituted dibenzothiophenes 16a/b respectively. A similar
iterative process was also successfully applied to 3d (See ESI
for details). While a higher catalyst loading and dilution were
required for the second iteration, the compatibility of this
approach with the flanking alkene and keto-functionality
highlights the potential of using intermolecular oxyarylation
Scheme 3 Use of substituted dibenzothiophene S-oxide.
The use of an ynamide under these reaction conditions did not
lead cleanly to the oxyarylation products, though the complex
mixture formed did indicate that
1 was functioning as an
effective oxidant. In order to benchmark the potential
suitability of dibenzothiophene-S-oxide as an oxidant in gold
catalysis it was applied under the conditions previously
reported by Davies and co-workers for the oxidative
transformation of ynamides using pyridine N-oxides (Scheme
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approaches with substantially more-functionalised sulfoxides. dibenzothiophene indole motif 18 7i
Journal Name
Thus an alternative is
.
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Ring-closing metathesis of dienes 16a
furnished the new proffered to the standard cross-couplinDgOsI:t1r0a.t1e0g39ie/Cs5rOeBq0u1i2r4in1Dg
symmetrical and unsymmetrical macrocyclic products 17a in prefunctionalisation of substrates for the formation of biaryl-
/b
/b
good yield, isolated as trans double bond isomers. The double linkages at the 4-position of dibenzothiophene. Second, a
bond geometry in 17a was determined to be trans through X- cascade process using 1,6-diyne 19 provides direct access into
ray crystallography (Figure 1).‡
the α-arylated cyclohexenone 20 in a single step (Scheme 6).
Gold-catalysed cycloisomerisation of the 1,5-ketoalkyne
generated from intermolecular oxyarylation results in
formation of five new bonds across the alkyne including three
carbon-carbon bonds at one carbon. The formation of
bisketone 21 as a side-product alongside the major product 20
is consistent with the hydration/aldol dehydration pathway
Davies and Detty-Mambo previously reported in
cycloisomerisation of alkynes tethered to unactivated,
enolisable ketones in the presence of cationic gold(I) species.36
Scheme 6 Utilising the introduced ketomethylene group in (a) formation of a
dibenzothienylindole as alternative to cross coupling, (b) cascade catalysis.
Scheme 5 The use of enynes in the oxyarylation process and application in an
iterative approach to access 4,6-disubstituted dibenzothiophenes and
subsequently macrocycles. a 2 mol% for 11a and 5 mol% for 11b-d
.
Conclusions
Conditions have been developed for regioselective formation
of Csp2-Csp3 bonds at the 4- and 6-positions of
dibenzothiophenes
without
prior
C-functionalisation.
Selectivity for the oxyarylation pathway is favoured by lower
temperature and electron-poor ligands on gold. The reactions
allow for the introduction of a variety of functionality under
robust, scalable conditions. Substantially more elaborate aryl
sulfoxides can be used in the oxyarylation approach as
demonstrated in an iterative application, which in conjunction
with enyne substrates was used to access new macrocyclic
structures. In addition, the use of the oxyarylation reaction as
the basis for further cascade process development has been
demonstrated.
Experimental†
Figure 1 Crystal structure of macocycle 17a with ellipsoids drawn at the 50%
probability level.
General Oxyarylation Procedure 1 (GP1), Table 2, Conditions A
The dibenzothiophene-S-oxide (1 eq.) and alkyne (2 eq.) were
stirred in toluene (0.1 M) until dissolved. The mixture was then
cooled in an ice bath at 0 oC and the catalyst, (2,4-di-tert-
butylC6H3O)3PAu(NCCH3)SbF6 (1-5 mol%), was added. The
reaction mixture was stirred until TLC showed consumption of
In addition to regiospecific formation of the Csp2-Csp3 bond
the simultaneous installation of a methylenecarbonyl moiety
introduces a potentially useful handle for elaboration. We
explored this in two ways: first, a classical Fischer-indole
synthesis from 3h (yield unoptimised, Scheme 6) affords the 3-
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dibenzothiophene-S-oxide, filtered through a pad of silica, 1H-NMR (300 MHz, CDCl3): δ = 8.04-7.96 (m, 1H), 7.93 (d, J 7.8,
View Article Online
DOI: 10.1039/C5OB01241D
washing with CH2Cl2 before being concentrated and the 1H), 7.74-7.66 (m, 1H), 7.38–7.26 (m, 3H), 7.15–6.93 (m, 6H),
residue purified by column chromatography.
3.78 (s, 2H), 2.79–2.63 (m, 4H); 13C-NMR (101 MHz, CDCl3): δ =
General Oxyarylation Procedure 2 (GP2), Table 2, Conditions B 206.3 (C), 140.9 (C), 140.0 (C), 139.0 (C), 136.2 (C), 136.1 (C),
The dibenzothiophene-S-oxide (1 eq.) and alkyne (2 eq.) were 128.9 (C), 128.6 (2CH), 128.5 (2CH), 128.0 (CH), 127.0 (CH),
stirred in toluene (0.01 M) until dissolved. The mixture was 126.2 (CH), 125.2 (CH), 124.7 (CH), 123.0 (CH), 122.0 (CH),
then cooled in a (NaCl/ice) bath to -10 oC and the catalyst, (2,4- 120.7 (CH), 49.6 (CH2), 43.7 (CH2), 29.9 (CH2); IR (neat): ν =
di-tert-butylC6H3O)3PAu(NCCH3)SbF6 (5 mol%) was added. The 3058, 3027, 2877, 1706, 1601, 1583, 1403, 1046, 746; HR-MS
reaction mixture was stirred for 6 hours at this temperature (ES-TOF): m/z: calcd for C22H18ONaS: 353.0976, found
and then allowed to warm to stir at rt for 14 hours, filtered 353.0991 [M + Na]+.
through a pad of silica washing with CH2Cl2 before being 1-(Dibenzo[b,d]thiophen-4-yl)-3-methoxypropan-2-one (3d)
concentrated and the residue purified by column Prepared according to GP1 using dibenzothiophene-S-oxide
1
chromatography. (40.0 mg, 0.2 mmol), methyl propargyl ether (33.8 µl, 0.4
Alkynes 11a, 3-(prop-2-yn-1-yloxy)prop-1-ene (54 wt% in mmol), toluene (2 mL) and catalyst (11.2 mg, 0.02 mmol, 5
o
Et2O), and 15, 4-(prop-2-yn-1-yloxy)but-1-ene (77 wt% in Et2O), mol%). The reaction was stirred for 45 minutes at 0 C. Column
were both used with a diethyl ether impurity.
1-(Dibenzo[b,d]thiophen-4-yl)hexan-2-one (3a)
Prepared according to GP1 using dibenzothiophene-S-oxide
chromatography (CH2Cl2) afforded 3d (47 mg, 87%) as a yellow
solid; Rf 0.31 (3:7 EtOAc:hexane); mp: 51–53 C; H-NMR (300
MHz, CDCl3): δ = 8.19–8.13 (m, 1H), 8.10 (d, J 7.7, 1H), 7.91–
o
1
1
(40.0 mg, 0.2 mmol), 1-hexyne (23 µl, 0.4 mmol), toluene (2 7.83 (m, 1H), 7.52–7.43 (m, 3H), 7.34 (d, J 7.2, 1H), 4.13 (s, 2H),
mL) and catalyst (11.2 mg, 0.02 mmol, 5 mol%). The reaction 4.03 (s, 2H), 3.41 (s, 3H); 13C-NMR (101 MHz, CDCl3): δ = 204.7
o
was stirred for 45 minutes at 0 C. Column chromatography (C), 140.0 (C), 138.9 (C), 136.2 (C), 136.1 (C), 128.2 (C), 128.1
(1:19 EtOAc:hexane) afforded 3a (49 mg, 87%) as a white solid; (CH), 127.1 (CH), 125.2 (CH), 124.7 (CH), 123.0 (CH), 122.0
o
1
Rf 0.28 (1:19 EtOAc:hexane); mp: 43-45 C; H-NMR (300 MHz, (CH), 122.0 (CH), 77.3 (CH2), 59.5 (CH3), 45.5 (CH2); IR (neat): ν
CDCl3): δ = 8.20–8.13 (m, 1H), 8.10 (d, J 7.2, 1H), 7.92–7.82 (m, = 2903, 1712, 1590, 1427, 1394, 1316, 1102, 759; HR-MS (ES-
1H), 7.51-7.43 (m, 3H), 7.32 (d, J 7.2, 1H), 3.96 (s, 2H), 2.51 (t, J TOF): m/z: calcd for C16H14O2NaS: 293.0612, found 293.0610
7.4, 2H), 1.63–1.50 (m, 2H), 1.33-1.19 (m, 2H), 0.85 (t, J 7.3, [M + Na]+. Open-flask protocol: To a 25 mL RBF under an
3H); 13C-NMR (101 MHz, CDCl3): δ = 207.5 (C), 140.0 (C), 139.1 atmosphere of air was added dibenzothiophene-S-oxide
1 (401
(C), 136.1 (C), 136.0 (C), 129.2 (C), 128.0 (CH), 127.0 (CH), mg, 2.0 mmol), methyl propargyl ether (338 µl, 4.0 mmol) and
125.2 (CH), 124.7 (CH), 123.0 (CH), 122.0 (CH), 120.6 (CH), 49.4 toluene (technical grade) (20 mL). The flask was placed in an
(CH2), 42.0 (CH2), 26.0 (CH2), 22.3 (CH2), 14.0 (CH3); IR (neat): ν ice bath and (2,4-di-tert-butylC6H3O)3PAu(NCCH3)SbF6 (22.4
= 3057, 2957, 2930, 2872, 1708, 1584, 1404, 749; HR-MS (ES- mg, 0.002 mmol, 1 mol%) was added. The reaction was stirred
TOF): m/z: calcd for C18H18ONaS: 305.0976, found 305.0978 at this temperature for 2 hours until TLC indicated reaction
[M + Na]+.
completion. Column chromatography (CH2Cl2) afforded 3d
(456 mg, 84%).
6-((tert-Butyldiphenylsilyl)oxy)-1-(dibenzo[b,d]thiophen-4-
6-Chloro-1-(dibenzo[b,d]thiophen-4-yl)hexan-2-one (3b)
Prepared according to GP1 using dibenzothiophene-S-oxide
1
(40.0 mg, 0.2 mmol), 6-chloro-1-hexyne (48.5 µL, 0.4 mmol), yl)hexan-2-one (3e)
toluene (2 mL) and catalyst (11.2 mg, 0.02 mmol, 5 mol%). The Prepared according to GP1 using dibenzothiophene-S-oxide
1
reaction was stirred for 45 minutes at
chromatography (9:11 CH2Cl2:hexane) afforded 3b as a yellow (336 mg, 1.0 mmol), toluene (5 mL) and catalyst (11.2 mg, 2
0
oC. Column (100 mg, 0.5 mmol), tert-butyl(hex-5-yn-1-yloxy)diphenylsilane
1
o
oil (50 mg, 79%); Rf 0.44 (9:11 CH2Cl2:hexane); H-NMR (300 mol%). The reaction was stirred for 2 hours at 0 C. Column
MHz, CDCl3): δ = 8.18–8.12 (m, 1H), 8.09 (dd, J 7.9 and 0.9, chromatography (3:2 hexane:CH2Cl2) afforded 3e (222 mg,
1H), 7.91–7.83 (m, 1H), 7.54–7.42 (m, 3H), 7.32 (d, J 7.2, 1H), 82%) as a viscous oil; Rf 0.31 (3:2 hexane:CH2Cl2); 1H-NMR (300
3.95 (s, 2H), 3.50–3.42 (m, 2H), 2.59–2.50 (m, 2H), 1.76–1.66 MHz, CDCl3): δ = 8.20–8.13 (m, 1H), 8.09 (dd, J 7.9 and 0.9,
(m, 4H); 13C-NMR (101 MHz, CDCl3): δ = 206.6 (C), 139.9 (C), 1H), 7.88-7.82 (m, 1H), 7.67–7.59 (m, 4H), 7.51–7.32 (m, 9H),
139.0 (C), 136.2 (C), 136.1 (C), 129.0 (C), 128.0 (CH), 127.0 7.30 (d, J 7.3, 1H), 3.93 (s, 2H), 3.60 (t, J 6.2, 2H), 2.51 (t, J 7.3,
(CH), 125.2 (CH), 124.8 (CH), 123.0 (CH), 122.0 (CH), 120.7 2H), 1.77–1.60 (m, 2H), 1.53–1.40 (m, 2H), 1.01 (s, 9H); 13C-
(CH), 49.4 (CH2), 44.7 (CH2), 41.1 (CH2), 31.8 (CH2), 21.1 (CH2); NMR (101 MHz, CDCl3): δ = 207.2 (C), 140.0 (C), 139.1 (C),
IR (neat): ν = 3060, 2953, 1711, 1584, 1443, 1401, 749; HR-MS 136.2 (C), 136.1 (C), 135.7 (4CH), 134.1 (2C), 129.7 (2CH), 129.2
(ES-TOF): m/z: calcd for C18H17ONaS35Cl: 339.0586, found (C), 128.0 (CH), 127.7 (4CH), 127.0 (CH), 125.2 (CH), 124.7 (CH),
339.0574 [M + Na]+.
123.0 (CH), 122.0 (CH), 120.6 (CH), 63.6 (CH2), 49.4 (CH2), 42.0
(CH2), 32.0 (CH2), 27.0 (3CH3), 20.4 (CH2), 19.4 (C); IR (neat): ν =
2930, 2856, 1713, 1588, 1427, 1105; HR-MS (ES-TOF): m/z:
1-(Dibenzo[b,d]thiophen-4-yl)-4-phenylbutan-2-one (3c)
Prepared according to GP1 using dibenzothiophene-S-oxide
1
(40.0 mg, 0.2 mmol), 4-phenyl-1-butyne (56 µl, 0.4 mmol), calcd for C34H36O2NaSiS: 559.2103, found 559.2102 [M + Na]+.
toluene (2 mL) and catalyst (11.2 mg, 0.02 mmol, 5 mol%). The 2-(3-(Dibenzo[b,d]thiophen-4-yl)-2-oxopropyl)isoindoline-1,3-
reaction was stirred for 45 minutes at
chromatography (1:1 hexane:CH2Cl2) afforded 3c (43 mg, 65%) Prepared according to GP1 using dibenzothiophene-S-oxide
as a white solid; Rf 0.78 (3:7 EtOAc:hexane); mp: 102-104 C; (200 mg, 1.0 mmol), N-propargyl phthalimide (370 mg, 2.0
0
oC. Column dione (3f)
1
o
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mmol) and catalyst (22.4 mg, 0.04 mmol, 2 mol%) for 4 hours mg, 40%) as white needles; Rf 0.20 (19:1 hexane:EtOAc); mp:
View Article Online
o
o
1
at 0 C and stirring for a further 16 hours at rt. The precipitate 93-95 C; H-NMR (300 MHz, CDCl3): δD=OI8: .1108.1–0389.1/C25O(mB0,1214H1D),
formed was washed with toluene and then recrystallized from 8.09 (dd, J 7.7 and 1.1, 1H), 7.89–7.82 (m, 1H), 7.64–7.59 (m,
hot EtOH affording 3f as yellow crystals (201 mg, 52 %); Rf 0.65 1H), 7.51–7.42 (m, 3H), 7.41–7.35 (m, 2H), 7.35–7.24 (m, 2H),
(3:7 EtOAc:hexane); mp: 190-192 oC (EtOH); 1H-NMR (300 MHz, 4.53 (s, 2H); 13C-NMR (101 MHz, CDCl3): δ = 200.2 (C), 141.4
CDCl3): δ = 8.20-8.15 (m, 1H), 8.13 (dd, J 7.9 and 1.0, 1H), 7.90– (C), 140.2 (C), 139.1 (C), 136.2 (C), 136.1 (2C), 133.7 (CH), 131.8
7.85 (m, 1H), 7.85–7.78 (m, 2H), 7.75–7.67 (m, 2H), 7.54–7.44 (CH), 128.8 (CH), 128.3 (CH), 127.6 (CH), 127.0 (CH), 125.1
(m, 3H), 7.40 (d, J 7.3, 1H), 4.56 (s, 2H), 4.11 (s, 2H); 13C-NMR (CH), 124.7 (CH), 123.0 (CH), 122.0 (CH), 120.8 (CH), 118.8(C),
(101 MHz, CDCl3): δ = 199.0 (C), 167.7 (2C), 140.0 (C), 139.0 48.7 (CH2); IR (neat): ν = 3054, 2940, 1703, 1591, 1441, 1332,
(C), 136.5 (C), 136.1 (C), 134.2 (2CH), 132.1 (2C), 128.0 (CH), 989, 742; HR-MS (ES-TOF): m/z: calcd for C20H14OS79Br:
127.5 (C), 127.2 (CH), 125.4 (CH), 124.8 (CH), 123.6 (2CH), 380.9949, found 380.9948 [M + H]+.
123.1 (CH), 122.0 (CH), 121.1 (CH), 46.7 (CH2), 46.3 (CH2); IR 2-(Dibenzo[b,d]thiophen-4-yl)-1-(4-methoxyphenyl)ethanone
(neat): ν = 2970, 1769, 1735, 1698, 1470, 1409, 1067; HR-MS (3j)
(ES-TOF): m/z: calcd for C23H15NO3NaS: 408.0670, found Prepared according to GP2 using dibenzothiophene-S-oxide
1
408.0667 [M + Na]+.
(40.0 mg, 0.2 mmol), 1-ethynyl-4-methoxybenzene (52 µl, 0.4
1-(Dibenzo[b,d]thiophen-4-yl)-3-hydroxydecan-2-one (3g)
Prepared according to GP1 using dibenzothiophene-S-oxide
mmol), toluene (20 mL) and catalyst (11.2 mg, 0.02 mmol, 5
mol%). Column chromatography (19:1 hexane:EtOAc) afforded
1
(40 mg, 0.2 mmol), dec-1-yn-3-ol (64 µl, 0.4 mmol), toluene (2 3j (28 mg, 42%) as a white solid; Rf 0.18 (19:1 hexane:EtOAc);
o
o
1
mL) and catalyst (11.2 mg, 5 mol%) for 4 hours at 0 C and mp: 113-115 C; H-NMR (300 MHz, CDCl3): δ = 8.19–8.12 (m,
stirring for a further 16 hours at rt. Purification of the reaction 1H), 8.11–8.01 (m, 3H), 7.90–7.82 (m, 1H), 7.51–7.39 (m, 3H),
mixture with column chromatography (9:1 hexane:EtOAc), 7.34 (d, J 7.2, 1H), 6.98–6.89 (m, 2H), 4.49 (s, 2H), 3.86 (s, 3H);
followed by recrystallization from hot MeOH afforded 3g (54 13C-NMR (101 MHz, CDCl3): δ = 195.0 (C), 163.8 (C), 139.8 (C),
o
1
mg, 76%); Rf 0.25 (9:1 hexane:EtOAc); mp: 52-54 C; H-NMR 139.1 (C), 136.3 (C), 136.2 (C), 131.0 (2CH), 129.9 (C), 129.7 (C),
(300 MHz, CDCl3): δ = 8.21– 8.14 (m, 1H), 8.11 (d, J 7.9, 1H), 127.8 (CH), 126.9 (CH), 125.1 (CH), 124.7 (CH), 123.0 (CH),
7.91–7.82 (m, 1H), 7.54–7.43 (m, 3H), 7.33 (d, J 7.2, 1H), 4.38 122.0 (CH), 120.4 (CH), 114.0 (2CH), 55.6 (CH3), 44.4 (CH2); IR
(dd, J 7.4 and 3.6, 1H), 4.07 (s, 2H), 3.33 (s, 1H), 2.02–1.88 (m, (neat): ν = 2910, 1717, 1593, 1508, 1400, 1167, 751; HR-MS
1H), 1.75–1.62 (m, 1H), 1.59–1.16 (m, 10H), 0.88 (t, J 6.6, 3H); (ES-TOF): m/z: calcd for C21H17O2NS: 333.0949, found 333.0950
13C-NMR (101 MHz, CDCl3): δ = 208.9 (C), 139.9 (C), 138.9 (C), [M + H]+.
136.3 (C), 136.1 (C), 128.1 (CH), 127.9 (C), 127.1 (CH), 125.2 2-(Dibenzo[b,d]thiophen-4-yl)-1-(thiophen-2-yl)ethanone (3k)
(CH), 124.8 (CH), 123.0 (CH), 122.0 (CH), 121.0 (CH), 76.4 (CH), Prepared according to GP2 using dibenzothiophene-S-oxide
1
44.3 (CH2), 34.0 (CH2), 31.9 (CH2), 29.5 (CH2), 29.2 (CH2), 24.9 (40 mg, 0.2 mmol), 2-ethynylthiophene (44 µl, 0.4 mmol),
(CH2), 22.8 (CH2), 14.2(CH3); IR (neat): ν = 3446, 2924, 2854, toluene (20 mL, 0.01 mmol) and catalyst (11.2 mg, 0.02 mmol,
1714, 1585, 1443, 1402, 1047, 749; HR-MS (ES-TOF): m/z: calcd 5 mol%). Purification of the reaction mixture by column
for C22H26O2NaS: 377.1551, found 377.1565 [M + Na]+.
2-(Dibenzo[b,d]thiophen-4-yl)-1-phenylethanone (3h)
Prepared according to GP2 using dibenzothiophene-S-oxide
chromatography (9:1 hexane:EtOAc) afforded 3k (38 mg, 62%)
as an orange oil; Rf 0.65 (9:1 hexane:EtOAc); 1H-NMR (300
MHz, CDCl3): δ = 8.19–8.11 (m, 1H), 8.09 (dd, J 7.5 and 1.2,
1
(60.0 mg, 0.3 mmol), phenylacetylene (65 µl, 0.6 mmol), 1H), 7.90–7.82 (m, 2H), 7.65 (dd, J 4.9 and 0.7, 1H), 7.51–7.38
toluene (0.01 M, 30 mL) and catalyst (16.8 mg, 0.03 mmol, 5 (m, 4H), 7.11 (dd, J 4.9 and 4.0, 1H), 4.46 (s, 2H); 13C-NMR (101
mol%). Column chromatography (19:1 hexane:EtOAc), MHz, CDCl3): δ = 189.2 (C), 143.9 (C), 139.9 (C), 138.9 (C), 136.2
followed by recrystallization from hot EtOAc afforded 3h (53 (C), 136.2 (C), 134.4 (CH), 132.9 (CH), 129.2 (C), 128.4 (CH),
mg, 58%) as a white solid; Rf 0.33 (19:1 hexane:EtOAc); mp: 127.8 (CH), 127.0 (CH), 125.1 (CH), 124.7 (CH), 123.0 (CH),
o
1
127-129 C; H-NMR (300 MHz, CDCl3): δ = 8.19–8.12 (m, 1H), 122.0 (CH), 120.7 (CH), 45.5 (CH2); IR (neat): ν = 3092, 3074,
8.12–8.05 (m, 3H), 7.89–7.82 (m, 1H), 7.63–7.54 (m, 1H), 7.52– 1641, 1410, 1276, 1057, 750; HR-MS (EI-TOF): m/z: calcd for
7.40 (m, 5H), 7.34 (d, J 6.9, 1H), 4.55 (s, 2H); 13C-NMR (101 C18H13OS2: 308.0330, found 308.0329 [M + H]+.
MHz, CDCl3): δ = 196.4 (C), 139.9 (C), 139.1 (C), 136.7 (C), 136.2 1-(2,8-Dibromodibenzo[b,d]thiophen-4-yl)-3-methoxypropan-
(2C), 133.5 (CH), 129.5 (C), 128.9 (2CH), 128.7 (2CH), 127.9 2-one (6)
(CH), 127.0 (CH), 125.1 (CH), 124.7 (CH), 123.0 (CH), 122.0 Sulfoxide
5 (71.6 mg, 0.2 mmol) was added to a 50 mL RBF
(CH), 120.6 (CH), 44.7 (CH2); IR (neat): ν = 3056, 2924, 2856, with methyl propargyl ether (34 µl, 0.4 mmol) and CHCl3 (30
1685, 1580, 1440, 1206, 908; HR-MS (ES-TOF): m/z: calcd for mL). catalyst (11.2 mg, 0.01 mmol, 5 mol%) was added and the
C20H14ONaS: 325.0663, found 325.0660 [M + Na]+.
1-(2-Bromophenyl)-2-(dibenzo[b,d]thiophen-4-yl)ethanone
(3i)
mixture was stirred at rt for 17 hours. Purification by column
chromatography (CH2Cl2) afforded
6 (58 mg, 70%) as a white
1
solid; Rf 0.07 (19:1 hexane:EtOAc); mp: 139-141 oC; H-NMR
Prepared according to GP2 using dibenzothiophene-S-oxide
1
(300 MHz, CDCl3): δ = 8.18 (s, 1H), 8.12 (s, 1H), 7.68 (d, J 8.5,
(40.0 mg, 0.2 mmol), 1-bromo-2-ethynylbenzene (50 µL, 0.4 1H), 7.56 (dd, J 8.5 and 1.3, 1H), 7.46 (s, 1H), 4.12 (s, 2H), 4.00
mmol), toluene (20 mL, 0.01 mmol) and catalyst (11.2 mg, 0.02 (s, 2H), 3.45 (s, 3H); 13C-NMR (101 MHz, CDCl3): δ = 204.1 (C),
mmol, 5 mol%). Column chromatography (19:1 hexane:EtOAc) 139.4 (C), 138.0 (C), 136.6 (C), 136.4 (C), 131.5 (CH), 130.6
followed by recrystallization from hot EtOH afforded 3i (30.5 (CH), 130.0 (C), 125.0 (CH), 124.3 (CH), 123.8 (CH), 119.1 (C),
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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119.0 (C), 77.6 (CH2), 59.6 (CH3), 44.8 (CH2); IR (neat): ν =, 7.5, 1H), 7.64–7.53 (m, 2H), 7.50 (td, J 7.5 and 0.9, 1H), 7.29 (d,
View Article Online
DOI: 10.1039/C5OB01241D
3067, 2901, 1723, 1567, 1410, 1319, 1072, 1042, 746; HR-MS J 7.6, 1H), 5.94 (ddt, J 17.2, 10.5 and 5.7, 1H), 5.32 (dd, J 17.2
(ES-TOF): m/z: calcd for C16H12O2NaS79Br81Br: 450.8802, found and 1.5, 1H), 5.24 (dd, J 10.5 and 1.2, 1H), 4.38–4.17 (m, 4H),
450.8801 [M + Na]+.
4.11 (d, J 5.8, 2H); 13C-NMR (101 MHz, CDCl3): δ = 204.6 (C),
1-(Allyloxy)-3-(dibenzo[b,d]thiophen-4-yl)propan-2-one (12a) 144.7 (C), 144.0 (C), 137.7 (C), 137.3 (C), 135.0 (C), 133.9 (CH),
Prepared according to GP1 using dibenzothiophene-S-oxide 132.7 (CH), 132.7 (CH), 131.7 (CH), 129.7 (CH), 127.5 (CH),
1
(100 mg, 0.5 mmol), 3-(prop-2-yn-1-yloxy)prop-1-ene 11a (54 122.2 (CH), 121.0 (CH), 118.3 (CH2), 75.1 (CH2), 72.7 (CH2), 42.5
wt% in Et2O, 177 mg, 1.0 mmol), and catalyst (11.2 mg, 0.02 (CH2); IR (neat): ν = 3050, 2857, 1725, 1551, 1485, 1424, 1321,
mmol, 2 mol%). The reaction mixture was stirred for 4 hours at 1161, 1145, 1070, 1045, 1012, 762; HR-MS (ES-TOF): m/z: calcd
o
0 C and left to warm to rt for a further 16 hours. Column for C18H17O3S: 313.0898, found 313.0906 [M + H]+.
chromatography (CH2Cl2) afforded 12a (119 mg, 80%) as a 3,3'-(Dibenzo[b,d]thiophene-4,6-diyl)bis(1-(allyloxy)propan-
yellow oil; Rf 0.34 (CH2Cl2); 1H-NMR (300 MHz, CDCl3): δ = 2-one) (16a)
8.19–8.14 (m, 1H), 8.10 (dd, J 7.9 and 1.0, 1H), 7.90–7.83 (m, Sulfoxide 14 (68 mg, 0.22 mmol) and enyne 11a (54 wt% in
1H), 7.52–7.43 (m, 3H), 7.35 (d, J 7.2, 1H), 5.89 (ddt, J 17.2, Et2O, 78.3 mg, 0.44 mmol) were dissolved in toluene (8.8 mL,
10.4 and 5.8, 1H), 5.27 (dd, J 17.2 and 1.5, 1H), 5.21 (dd, J 10.4 0.025 M). After stirring for 20 minutes the reaction mixture
and 1.5, 1H), 4.18 (s, 2H), 4.06 (s, 2H), 4.06–4.02 (m, 2H); 13C- was transferred to an ice bath at
0
oC. (2,4-Di-tert-
NMR (101 MHz, CDCl3): δ = 205.0 (C), 140.0 (C), 139.0 (C), butylC6H3O)3PAu(NCCH3)SbF6 (12.3 mg, 0.011 mmol, 5 mol%)
136.2 (C), 136.1 (C), 133.8 (CH), 128.3 (C), 128.1 (CH), 127.0 was added with a further portion (6.1 mg, 5.5 μmol, 2.5 mol%)
(CH), 125.2 (CH), 124.7 (CH), 123.0 (CH), 122.0 (CH), 120.8 added after 3 hours with the reaction mixture then stirred for
(CH), 118.3 (CH2), 74.8 (CH2), 72.6 (CH2), 45.6 (CH2); IR (neat): ν a further 1 hour at 0 oC. The reaction mixture was filtered
= 2901, 1726, 1554, 1443, 1402, 1096, 912; HR-MS (ES-TOF): through a plug of silica and washed with CH2Cl2 (10 mL). The
m/z: calcd for C18H16O2SNa: 319.0769, found 319.0775 [M + reaction mixture was concentrated under reduced pressure
Na]+.
and purified by column chromatography (4:1 hexane:EtOAc)
N-Allyl-N-(3-(dibenzo[b,d]thiophen-4-yl)-2-oxopropyl)-4-
methylbenzenesulfonamide (12c)
Prepared according to GP1 using dibenzothiophene-S-oxide
providing 16a (65 mg, 73%) as a white solid; Rf 0.58 (1:1
hexane:EtOAc); mp: 77-80 C; H-NMR (300 MHz, CDCl3): δ =
8.08 (d, J 7.7, 2H), 7.47 (app t, J 7.6, 2H), 7.34 (d, J 7.2, 2H),
o
1
1
(40 mg, 0.2 mmol), N-allyl-4-methyl-N-(prop-2-yn-1- 5.90 (ddt, J 17.2, 10.4 and 5.7, 2H), 5.27 (app d, J 17.2, 2H),
yl)benzenesulfonamide 11c (96 mg, 0.4 mmol), and catalyst 5.21 (app d, J 10.4, 2H) 4.17 (s, 4H), 4.11-4.01 (m, 8H); 13C-
(11.2 mg, 0.02 mmol, 5 mol%). The reaction mixture was NMR (101 MHz, CDCl3): δ = 204.8 (2C), 139.5 (2C), 136.6 (2C),
stirred for 2.5 hours at 0 oC. Column chromatography (9:1 133.8 (2CH), 128.3 (2CH), 128.3 (2C), 125.4 (2CH), 121.0 (2CH),
hexane:EtOAc) followed by recrystallization from hot MeOH 118.3 (2CH2), 74.8 (2CH2), 72.6 (2CH2), 45.6 (2CH2); IR (neat): ν
afforded 12c (66 mg, 74%) as a white solid; Rf 0.31 (9:1 = 2855, 1722, 1574, 1426, 1390, 1331, 1164, 1060, 1045; HR-
hexane:EtOAc); mp: 104-106 oC; 1H NMR (300 MHz, CDCl3): δ = MS (ES-TOF): m/z: calcd for C24H24O4NaS: 431.1293, found
8.21–8.14 (m, 1H), 8.11 (dd, J 8.1, 0.9, 1H), 7.91–7.82 (m, 1H), 431.1288 [M + Na]+.
7.65 (d, J 8.3, 2H), 7.53–7.43 (m, 3H), 7.32 (d, J 7.2, 1H), 7.21 1-(Allyloxy)-3-(6-(3-(but-3-en-1-yloxy)-2-
(d, J 8.1, 2H), 5.58 (ddt, J 16.9, 10.1 and 6.8, 1H), 5.03 (dd, J oxopropyl)dibenzo[b,d]thiophen-4-yl)propan-2-one (16b)
10.1, 1.1, 1H), 4.96 (dd, J 16.9, 1.1, 1H) 4.10 (s, 2H), 4.01 (s, Sulfoxide 14 (60 mg, 0.192 mmol) and enyne 15 (77 wt% in
2H), 3.78 (d, J 6.7, 2H), 2.36 (s, 3H); 13C-NMR (101 MHz, CDCl3): Et2O, 50 mg, 0.348 mmol) were dissolved in toluene (0.025 M,
δ = 201.9 (C), 143.7 (C), 140.0 (C), 139.0 (C), 136.3 (C), 136.2 10 mL). After stirring for 20 minutes at rt the reaction was
(C), 136.0 (C), 132.1 (CH), 129.8 (2CH), 128.2 (CH), 128.0 (C), transferred to an ice bath at
0
oC and (2,4-di-tert-
127.6 (2CH), 127.1 (CH), 125.3 (CH), 124.8 (CH), 123.0 (CH), butylC6H3O)3PAu(NCCH3)SbF6 (7.5 mol%) was added. The
122.0 (CH), 120.9 (CH), 120.5 (CH2) 54.4 (CH2), 51.4 (CH2), 46.4 reaction was stirred for 4 hours filtered through a pad of silica
(CH2), 21.6 (CH3); IR (neat): ν = 1731, 1443, 1397, 1153, 1045, washing with CH2Cl2, concentrated and purified by column
924, 752; HR-MS (ES-TOF): m/z: calcd for C25H24NO3S2: chromatography (4:1 hexane:EtOAc) to afford 16b (68 mg,
450.1198, found 450.1180 [M + H]+.
1-(Allyloxy)-3-(5-oxidodibenzo[b,d]thiophen-4-yl)propan-2-
one (14)
83%) as an off white solid; Rf 0.81 (1:1 hexane:EtOAc); mp: 57-
59 C; H-NMR (300 MHz, CDCl3): δ = 8.02 (dd, J 7.9 and 0.8,
2H), 7.40 (app t, J 7.6, 2H), 7.28 (d, J 7.3, 2H), 5.91–5.68 (m,
o
1
mCPBA (72.3 mg, 0.42 mmol, 1.1 equiv) was added in 5 2H), 5.21 (dd, J 17.2 and 1.6, 1H), 5.15 (dd, J 10.2 and 1.6, 1H),
portions over 10 minutes to a solution of 12a (113 mg, 0.38 5.04 (dd, J 17.2 and 1.6, 1H), 4.97 (dd, J 10.2 and 1.6, 1H), 4.10
o
mmol) in CH2Cl2 (10 mL) at 0 C. The reaction was allowed to (s, 4H), 4.02–3.96 (m, 6H), 3.48 (t, J 6.7, 2H), 2.37–2.27 (m,
warm to rt over 2 hours, washed with NaHCO3 (4 × 10 mL), 2H); 13C-NMR (101 MHz, CDCl3): δ = 205.1 (C), 204.9 (C), 139.6
extracted with CH2Cl2 (4 × 10 mL), dried over Na2SO4, filtered (2C), 136.7 (2C), 134.9 (CH), 133.8 (CH), 128.3 (2CH), 128.2
and concentrated under reduced pressure. Purification by (2C), 125.4 (2CH), 121.0 (2CH), 118.3 (CH2), 117.0 (CH2), 75.9
column chromatography (4:1 hexane:EtOAc to EtOAc) afforded (CH2), 74.8 (CH2), 72.6 (CH2), 71.3 (CH2), 45.6 (2CH2), 34.2
firstly 12a (25 mg, 22%) and then 14 (74 mg, 62%) as a white (CH2); IR (neat): ν = 2860, 1721, 1644, 1575, 1476, 143, 1061,
o
1
solid; Rf 0.37 (3:7 hexane:EtOAc); mp: 98-100 C; H-NMR (300 913, 776; HR-MS (ES-TOF): m/z: calcd for C25H26O4NaS:
MHz, CDCl3): δ = 7.96 (d, J 7.5, 1H), 7.80 (d, J 7.6, 1H), 7.74 (d, J 445.1450, found 445.1429 [M + Na]+.
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Organic & Biomolecular Chemistry
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Journal Name
Macrocycle 17a
[1,3-Bis-(2,4,6-trimethylphenyl)-2-
imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylp
HR-MS (ES-TOF): m/z: calcd for C26H18NS: 376.1160, found
View Article Online
DOI: 10.1039/C5OB01241D
376.1170 [M + H]+.
Diethyl
4-(dibenzo[b,d]thiophen-4-yl)-3-methyl-5-
hosphine)ruthenium (10.4 mg, 0.012 mmol) was added to a oxocyclohex-3-ene-1,1-dicarboxylate (20) and diethyl 2-(3-
solution of 16a (100 mg, 0.245 mmol) in CH2Cl2 (25 mL). The (dibenzo[b,d]thiophen-4-yl)-2-oxopropyl)-2-(2-
reaction mixture was heated to reflux for 1 hour, allowed to oxopropyl)malonate (21)
cool, concentrated and purified by column chromatography Prepared according to GP1 using dibenzothiophene-S-oxide
1
(3:7 hexane:EtOAc) to afford 17a (80 mg, 86%) as a white solid; (40 mg, 0.2 mmol), diyne 19 (48.6 mg, 0.4 mmol), toluene (2
Rf 0.58 (1:1 hexane:EtOAc); mp: 165-167 oC; 1H-NMR (300 mL) and catalyst (11.2 mg, 5 mol%). The reaction was stirred
o
MHz, CDCl3): δ = 8.08 (d, J 7.2, 2H), 7.48 (app t, J 7.6, 2H), 7.39 for 2 hours at 0 C before allowing to warm to rt for 17 hours.
(d, J 7.0, 2H), 5.74–5.60 (m, 2H), 4.19 (s, 4H), 4.02 (s, 4H), 3.96 Column chromatography (3:7 hexane:CH2Cl2 to CH2Cl2)
(dd, J 3.0 and 1.3, 4H); 13C-NMR (101 MHz, CDCl3): δ = 205.0 afforded 20 (49 mg, 57%) as a colourless oil and 21 (15 mg,
(2C), 139.2 (2C), 136.7 (2C), 130.2 (2CH), 128.1 (2CH), 128.1 17%) as a colourless oil.
1
(2C), 125.7 (2CH), 121.1 (2CH), 74.3 (2CH2), 71.1 (2CH2), 45.6 20 Rf 0.48 (3:7 hexane:EtOAc); H NMR (300 MHz, CDCl3): δ =
(2CH2); IR (neat): ν = 2855, 1722, 1574, 1426, 1390, 1331, 8.13 (ddd, J 12.9, 5.7 and 2.4, 2H), 7.83–7.75 (m, 1H), 7.55–
1144, 1060, 1045, 919, 776, 731; HR-MS (ES-TOF): m/z: calcd 7.37 (m, 3H), 7.11 (dd, J 7.2 and 1.0, 1H), 4.44–4.21 (m, 4H),
for C22H20O4NaS: 403.0980, found 403.0996 [M + Na]+.
Macrocycle 17b
[1,3-Bis-(2,4,6-trimethylphenyl)-2-
imidazolidinylidene]dichloro(phenylmethylene)(tricyclohexylp
3.32-2.94 (m, 4H), 1.85 (s, 3H), 1.32 (t, J 7.1, 3H), 1.31 (t, J 7.1,
3H),; 13C NMR (101 MHz, CDCl3): δ = 192.4 (C), 169.9 (C), 169.8
(C) 156.3 (C), 156.3 (C), 140.1 (C), 139.4 (C), 136.1 (C), 136.1 (C)
135.8 (C), 128.2 (CH), 126.8 (CH), 124.7 (CH), 124.5 (CH), 122.8
hosphine)ruthenium (5.0 mg, 0.006 mmol) was added to a (CH), 121.8 (CH), 121.0 (CH), 62.6 (CH2), 62.4 (CH2), 55.0 (C),
solution of 16b (50 mg, 0.118 mmol) in CH2Cl2 (25 mL). The 42.6 (CH2), 37.5 (CH2), 22.7 (CH3), 14.2 (2CH3); IR (neat): ν =
reaction mixture was heated to reflux for
2 hours, 2982, 1729, 1673, 1302, 1250, 1167, 752; HR-MS (ES-TOF):
concentrated and purified by column chromatography (3:7 m/z: calcd for C25H24O5NaS: 459.1242, found 459.1229 [M +
hexane:EtOAc) to afford 17b (35 mg, 70%) as a white solid; Rf Na]+.
o
1
1
0.48 (1:1 hexane:EtOAc); mp: 138-139 C; H-NMR (300 MHz, 21 Rf 0.42 (7:3 hexane:EtOAc); H NMR (300 MHz, CDCl3): δ =
CDCl3): δ = 8.07 (d, J 7.8, 2H), 7.48 (td, J 7.6 and 3.1, 2H), 7.37 8.18–8.12 (m, 1H), 8.09 (dd, J 7.9 and 0.9, 1H), 7.87–7.81 (m,
(d, J 5.1, 2H), 6.11–5.95 (m, 1H), 5.69 (dt, J 15.0 and 5.6, 1H), 1H), 7.50–7.42 (m, 3H), 7.31 (d, J 7.0, 1H), 4.13 (q, J 7.1, 2H),
4.18 (s, 4H), 4.15-4.05 (m, 6H), 3.64 (t, J 5.8, 2H), 2.42 (dd, J 4.12 (q, J 7.1, 2H), 3.97 (s, 2H), 3.50 (s, 2H), 3.31 (s, 2H), 1.99
11.6 and 5.6, 2H); 13C-NMR (101 MHz, CDCl3): δ = 206.6 (C), (s, 3H), 1.17 (t, J 7.0, 6H); 13C NMR (101 MHz, CDCl3): δ = 206.0
205.8 (C), 139.2 (C), 139.1 (C), 136.7 (C), 136.6 (C), 132.0 (CH), (C), 204.6 (C), 169.5 (2C), 139.9 (C), 139.1 (C), 136.3 (C), 136.0
128.7 (CH), 128.7 (CH), 128.4 (C), 128.4 (C) 127.4 (CH), 125.4 (C), 128.4 (CH), 128.2 (C), 127.1 (CH), 125.3 (CH), 124.8 (C),
(2CH), 121.0 (CH), 120.9 (CH), 76.3 (CH2), 74.4 (CH2), 71.7 122.9 (C), 122.0 (CH), 120.8 (CH), 62.1 (2CH2), 53.2 (C), 49.4
(CH2), 71.2 (CH2), 44.7 (CH2), 44.2 (CH2), 32.8 (CH2); IR (neat): ν (CH2), 45.8 (CH2), 44.9 (CH2), 30.2 (CH3), 14.0 (2CH3); IR (neat):
= 2861, 1720, 1644, 1575, 1426, 1143, 1062, 914, 775; HR-MS ν = 2982, 2930, 1719, 1444, 1403, 1364, 1201, 1096, 754; HR-
(ES-TOF): m/z: calcd for C23H22O4NaS: 417.1137, found MS (ES-TOF): m/z: calcd for C25H26O6SNa: 477.1348, found
417.1136 [M + Na]+.
477.1339 [M + Na]+.
3-(Dibenzo[b,d]thiophen-4-yl)-2-phenyl-1H-indole (18)
To 3h (55 mg, 0.183 mmol, 1.0 eq.) was added AcOH (0.80 ml),
TFA (0.28 ml) and phenylhydrazine (45 µL, 0.46 mmol, 2.5 eq.)
in a sealed (Ace) tube. The reaction was stirred at 100 oC for 28
hours at which point reaction completion was observed by
TLC. The mixture was added to ice/water (10 mL), the mixture
was extracted with CH2Cl2 (10 mL × 3) and the organic portions
were washed with HCl (1 M, 5 mL), water (5 mL), dried over
Na2SO4, concentrated and purified by column chromatography
(9:1 hexane:EtOAc) to afford 18 (45.6 mg, 66%) as a viscous
orange oil; Rf 0.31 (9:1 hexane:EtOAc); 1H-NMR (300 MHz,
CDCl3): δ = 8.46 (s, 1H), 8.21 (ddd, J 7.6, 5.6 and 1.4, 2H), 7.77–
7.70 (m, 1H), 7.59–7.48 (m, 3H), 7.48–7.41 (m, 3H), 7.40–7.34
(m, 2H), 7.33–7.20 (m, 4H), 7.13 (td, J 7.6 and 0.9, 1H); 13C-
NMR (101 MHz, CDCl3): δ = 141.4 (C), 140.1 (C), 136.1 (C),
136.0 (2C), 134.8 (C), 132.5 (C), 130.5 (C), 129.3 (CH), 128.9
(2CH), 128.8 (C), 127.9 (CH), 127.3 (2CH), 126.7 (CH), 125.0
(CH), 124.3 (CH), 123.0 (CH), 122.9 (CH), 121.8 (CH), 120.4
(CH), 120.4 (CH), 120.3 (CH), 113.5 (C), 111.1 (CH); IR (neat): ν
= 3408, 3057, 1578, 1487, 1442, 1384, 1253, 905, 742, 693;
Acknowledgements
The authors thank Dr. Louise Male (University of Birmingham)
for X-ray crystallography and the EPSRC/University of
Birmingham for financial support (studentship to MJB). The
facilities used in this research were part supported through
Birmingham Science City AM2 by Advantage West Midlands
and the European Regional Development Fund.
Notes and references
‡ Crystal structure determination of 17a. Crystal Data for C22H20O4S,
M =380.44, triclinic, space group P-1 (no. 2), a = 9.0122(4) Å, b =
10.2941(6) Å, c = 10.6266(6) Å, α = 75.079(5)°, β = 73.655(4)°, γ =
75.040(5)°, V = 895.60(9) Å3, Z = 2, T = 100.00(10) K, μ(CuKα) =
1.826 mm-1, Dcalc = 1.411 g/cm3, 4979 reflections measured (8.85°
≤ 2Θ ≤ 136.478°), 3193 unique (Rint = 0.0141, Rsigma = 0.0201) which
were used in all calculations. The final R1 was 0.0290 (I > 2σ(I)) and
wR2 was 0.0733 (all data). CCDC 1405198.
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§ Yield of known compounds 8 and 10 determined by 1H NMR
against an internal standard.
Taneda, H. Hayashi, A. Sakushima, K. Kamata, A. K. Suzuki, S.
Yoshino, M. Sakata, M. Sagai, and K.-I. Seki,ViBewioAl.rticPlehOanrlmine.
DOI: 10.1039/C5OB01241D
Bull., 2002, 25, 145-146.; l) D. A. Patrick, J. E. Hall, B. C.
Bender, D. R. McCurdy, W. D. Wilson, F. A. Tanious, S. Saha
and R. R. Tidwell, Eur. J. Med. Chem., 1999, 34, 575-583; m)
A. M. El-Naggar, F. S. M. Ahmed and S. G. Donia, J. Indian
Chem. Soc., 1983, 60, 479-482.
1
For recent examples see: a) S.-C Dong, L. Zhang, J. Liang, L.-S.
Cui, Q. Li, Z.-Q. Jiang, L.-S. Liao, J. Phys. Chem. C., 2014, 118
,
2375-2384; b) L. Yao, S. Sun, S. Xue, S. Zhang, X. Wu, H.
Zhang, Y. Pan, C. Gu, F. Li and Y. Ma, J. Phys. Chem. C., 2013,
117, 14189-14196; c) L. Yu, J. Liu, S. Hu, R. He, W. Yang, H.
Wu, J. Peng, R. Xia and D. D. C. Bradley, Adv. Funct. Mater.,
2013, 23, 4366–4376; d) L. Ying, Y.-H. Li, C.-H. Wei, M.-Q.
Wang, W. Yang, H.-B. Wu and Y. Cao, Chin. J. Polym. Sci.,
2013, 31, 88-97; e) S. Cai, X. Hu, J. Han, Z. Zhang, X. Li, C.
Wang and J. Su, Tetrahedron., 2013, 69, 1970-1977.
D. Vasu, H. Yorimitsu and A. Osuka, Angew. Chem., Int. Ed.,
2015, 54, 7162-7166.
8
a) X.-D. Xiong, C.-L. Deng, X.-S. Peng, Q. Miao and H. N. C.
Wong, Org. Lett., 2014, 16, 3252−3255; b) P. Zhao, H. Yin, H.
Gao and C. Xi, J. Org. Chem., 2013, 78, 5001-5006; c) T. H.
Jepsen, M. Larsen, M. Jørgensen, and M. B. Nielsen,
Synthesis, 2013, 45, 1115-1120; d) X. Shang, W. Chen and Y.
Yao, Synlett, 2013, 24, 851-854; V. B. Pandya, M. R. Jain, B. V.
Chaugule, J. Patel, B. M. Parmar, J. K. Joshi and P. R. Patel,
2
3
Synth. Commun., 2012, 42
, 497-505; e) S. Rodriguez-
a) T. Umemoto and S. Ishihara, J. Am. Chem. Soc., 1993, 115
,
Aristegui, K. M. Clapham, L. Barrett, C. Cano, M. D. -E. Murr,
R. J. Griffin, I. R. Hardcastle, S. L. Payne, T. Rennison, C.
2156-2164; b) C. Zhang, Org. Biomol. Chem., 2014, 12, 6580–
6589.
Richardson and B. T. Golding, Org. Biomol. Chem., 2011, 9,
4
a) J. Korang, W. R. Grither and R. D. McCulla, J. Am. Chem.
Soc., 2010, 132, 4466–4476; b) M. Nag and W. S. Jenks, J.
Org. Chem., 2005, 70, 3458-3463; c) M. Nag and W. S. Jenks,
J. Org. Chem., 2004, 69, 8177–8182; d) A. B. Thomas and A.
Greer, J. Org. Chem., 2003, 68, 1886–1891; e) D. D. Gregory,
Z. Wan and W. S. Jenks, J. Am. Chem. Soc., 1997, 119, 94–
6066-6074; f) R. Samanta and A. P. Antonchick, Angew.
Chem., Int. Ed., 2011, 50, 5217-5220; g) T. H. Jepsen, M.
Larsen, M. Jørgensen, K. A. Solanko, A. Bond, A. Kadziola and
M. B. Nielsen, Eur. J. Org. Chem., 2011, 53–57; h) M. Kienle,
A. Unsinn and P. Knochel, Angew. Chem., Int. Ed., 2010, 49
4751–4754.
,
102; f) Z. Wan and W. S. Jenks, J. Am. Chem. Soc., 1995, 117
2667–2668.
,
9
a) R. Che, Z. Wu, Z. Li, H. Xiang and X. Zhou, Chem. Eur. J.,
2014, 20, 7258-7261; b) S. Trosien, P. Bꢀttger and S. R.
Waldvogel, Org. Lett., 2014, 16, 402−405; c) P. Saravanan
and P. Anbarasan, Org. Lett., 2014, 16, 848−851; d) T. Wesch,
A. Berthelot-Bréhier, F. R. Leroux and F. R. Colobert, Org.
Lett., 2013, 15, 2490-2493; e) J. Chen and T. Murafuji,
Organometallics, 2011, 30, 4532–4538; f) X. Xu, X. Li, A.
Wang, Y. Sun, W. B. Schweizer and R. Prins, Helv. Chim. Acta
2011, 94, 1754-1763; g) M. Black, J. I. G. Cadogan and H.
5
a) V. Desikan, Y. Liu, J. P. Toscano and W. S. Jenks, J. Org.
Chem., 2007, 72, 6848-6859; b) V. Desikan, Y. Liu, J. P.
Toscano and W. S. Jenks, J. Org. Chem., 2008, 73, 4398-4414;
c) T. Nakahodo, M. Okuda, H. Morita, T. Yoshimura, M. O.
Ishitsuka, T. Tuchiya, Y. Maeda, H. Fujihara, T. Akasaka, X.
Gao and S. Nagase, Angew. Chem., Int. Ed., 2008, 47, 1298–
1300; d) H. Morita, A. Tatami, T. Maeda, B. J. Kim, W.
Kawashima, T. Yoshimura, H. Abe and T. Akasaka, J. Org.
Chem., 2008, 73, 7159–7163.
McNab, Org. Biomol. Chem., 2010, 8, 2961-2967; h) R. Sanz,
Y. Fernández, M. P. Castroviejo, A. Pérez and F. J. Fañanás, J.
Org. Chem., 2006, 71, 6291-6294.
6
7
a) W. S. Jenks, M. J. Heying, S. A. Stoffregen and E. M.
Rockafellow, J. Org. Chem., 2009, 74, 2765-2770; b) S. A. 10 a) M. Nandakumar, J. Karunakaran and A. K.
Stoffregen, M. J. Heying and W. S. Jenks, J. Am. Chem. Soc.,
2007, 129, 15746-15747.
a) Y. Gao, K. J. Kellar, R. P. Yasuda, T. Tran, Y. Xiao, R. F.
Dannals and A. G. Horti, J. Med. Chem., 2013, 56, 7574−7589;
b) C. Cano, K. Saravanan, C. Bailey, J. Bardos, N. J. Curtin, M.
Frigerio, B. T. Golding, I. R. Hardcastle, M. G. Hummersone,
K. A. Menear, D. R. Newell, C. J. Richardson, K. Shea, G. C. M.
Mohanakrishnan, Org. Lett., 2014, 16, 3068-3071; b) S.-M. T.
Toguem, I. Malik, M. Hussain, J. Iqbal, A. Villinger and P.
Langer, Tetrahedron., 2013, 69, 160-173; c) A. S. K. Hashmi,
W. Yang and F. Rominger, Chem. Eur. J., 2012, 18, 6576-
6580; d) S.-M. T. Toguem, I. Knepper, P. Ehlers, T. T. Dang, T.
Patonay and P. Langer, Adv. Synth. Catal., 2012, 354, 1819-
1826.
Smith, P. Thommes, A. Ting and R. J. Griffin, J. Med. Chem., 11 W. Yang, Q. Hou, C. Liu, Y. Niu, J. Huang, R. Yang and Y. Cao,
2013., 56, 6386−6401; c) J. Korang, I. Emahi, W. R. Grither, S. J. Mater. Chem., 2003, 13, 1351-1355.
M. Baumann, D. A. Baum and R. D. McCulla, RSC Adv., 2013, 12 H. Sirringhaus, R. H. Friend, C. Wang, J. Leuningerb and K. J.
, 12390–12397; d) M. R. Schrimpf, K. B. Sippy, C. A. Briggs, Müllen, J. Mater. Chem., 1999, , 2095-2101.
D. J. Anderson, T. Li, J. Ji, J. M. Frost, C. S. Surowy, W. H. 13 A. R. Katritzky and S. J. Perumal, J. Heterocycl. Chem., 1990,
Bunnelle, M. Gopalakrishnan and M. D. Meyer, Bioorg. Med. 27, 1737-1740.
Chem. Lett., 2012, 22, 1633–1638; e) M. Zhang, G. E. 14 K. Groll, T. D. Blake, A. Unsinn, D. Haas and P. Knochel,
Ravilious, L. M. Hicks, J. M. Jez and R. D. McCulla, J. Am. Angew. Chem., Int. Ed., 2012, 51, 11157-11161.
3
9
Chem. Soc., 2012, 134, 16979−16982; f) S. R. Patpi, L. 15 a) C. Figliola, L. Male, S. L. Horswell and Richard S. Grainger,
Pulipati, P. Yogeeswari, D. Sriram, N. Jain, B. Sridhar, R.
Murthy, T. A. Devi, S. V. Kalivendi and S. J. Kantevari, J. Med.
Chem., 2012, 55, 3911−3922; g) C. Cano, O. R. Barbeau, C.
Bailey, X.-L. Cockcroft, N. J. Curtin, H. Duggan, M. Frigerio, B.
T. Golding, I. R. Hardcastle, M. G. Hummersone, C. Knights, K.
A. Menear, D. R. Newell, C. J. Richardson, G. C. M. Smith, B.
Spittle and R. J. Griffin, J. Med. Chem., 2010, 53, 8498-8507;
h) W. Kemnitzer, N. Sirisoma, S. Jiang, S. Kasibhatla, C.
Crogan-Grundy, B. Tseng, J. Drewe and S. X. Cai, Bioorg. Med.
Chem. Lett., 2010, 20, 1288-1292; i) M.-J. R. P. Queiroz, A. S.
Abreu, M. S. D. Carvalho, P. M. T. Ferreira, N. Nazareth and
M. S.-J. Nascimento, Bioorg. Med. Chem., 2008, 16, 5584-
5589; j) J. J. J. Leahy, B. T. Golding, R. J. Griffin, I. R.
Eur. J. Inorg. Chem., DOI:10.1002/ejic.201500355; b) C.
Figliola, L. Male, P. N. Horton, M. B. Pitak, S. J. Coles, S. L.
Horswell and R. S. Grainger, Organometallics, 2014, 33
,
4449–4460; c) S. Allenmark, R. S. Grainger, S. Olsson and B.
Patel, Eur. J. Org. Chem., 2011, 4089-4092; d) B. Patel, J.
Carlisle, S. E. Bottle, G. R. Hanson, B. M. Kariuki, L. Male, J. C.
McMurtrie, N. Spencer and R. S. Grainger, Org. Biomol.
Chem., 2011,
Kariuki, L. Male and N. Spencer, J. Am. Chem. Soc., 2011, 133
5843-5852; f) R. S. Grainger, B. Patel and B. M. Kariuki,
9, 2336-2344; e) R. S. Grainger, B. Patel, B. M.
,
Angew.,Chem. Int. Ed., 2009, 48, 4832-4835; g) R. S.
Grainger, A. Procopio and J. W. Steed, Org. Lett., 2001, 3,
3565-3568.
Hardcastle, C. Richardson, L. Rigoreau and G. C. M. Smith, 16 Representative examples: a) M. Garzon and P. W. Davies,
Bioorg. Med. Chem. Lett., 2004, 14, 6083–6087; k) Y. Mori, S.
Org. Lett., 2014, 16, 4850-4853; b) H. V. Adcock, T. Langer
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and P. W. Davies, Chem. Eur. J., 2014, 20, 7262-7266; c) M. 26 For a rationalisation of decreasing temperature to slow
View Article Online
Dos Santos and P. W. Davies, Chem. Commun., 2014, 50
6001-6003; d) E. Chatzopoulou and P. W. Davies, Chem.
Commun., 2013, 49, 8617-8619; e) P. W. Davies and S. J.-C.
,
down elimination of the nucleofuge in related nitrenoid
DOI: 10.1039/C5OB01241D
chemistry see: B. Lu, Y. Luo, L. Liu, L. Ye, Y. Wang and L.
Zhang, Angew. Chem., Int. Ed., 2011, 50, 8358-8362.
Albrecht, Synlett, 2012, 23, 70-73; f) P. W. Davies, A. 27 The role of the phosphite ligand to allow reaction at a vinyl
Cremonesi and L. Dumitrescu, Angew. Chem., Int. Ed., 2011,
50, 8931-8934; g) P. W. Davies and S. J.-C. Albrecht, Chem.
Commun., 2008, 42, 238-240.
gold carbenoid centre by disfavouring elimination of a
nucleofuge to form the gold carbene centre was employed
to rationalise chemoselectivity for intermolecular trapping
pathways in gold-catalysed ynamide oxidation reaction. See
ref 16c.
17 Alkyne oxyarylation using S-oxides: a) N. D. Shapiro, F. D.
Toste, J. Am. Chem. Soc., 2007, 129, 4160−4161; b) G. Li and
L. Zhang, Angew. Chem., Int. Ed., 2007, 46, 5156−5159; c) A. 28 C. H. M. Amijis, V. López-Carillo, M. Raducan, P. Pérez-Galán,
B. Cuenca, S. Montserrat, K. M. Hossain, G. Mancha, A.
Lledόs, M. Mediό-Simon, G. Ujaque, G. Asensio, Org. Lett.,
C. Ferrer and A. M. Echavarren, J. Org. Chem., 2008, 73,
7721-7730.
2009, 11, 4906-4909; d) C. Li, K. Pati, G. Lin, S. Md, A. Sohel, 29 The use of hex-1-yn-1-ylbenzene gave the α-β unsaturated
H.-H Hung and R.-S. Lui, Angew. Chem., Int. Ed., 2010, 49
,
ketone in a 58% yield (based on the dibenzothiophene-S-
9891-9894; e) B. Lu, Y. Li, Y. Wang, D. H. Aue, Y. Luo, and L.
oxide)
Zhang J. Am. Chem. Soc. 2013, 135, 8512−8524; f) R. Fang 30 L. Ye, W. He and L. Zhang, J. Am. Chem. Soc., 2010, 132
,
and L. Yang, Organometallics, 2012, 31, 3043-3055.
18 For recent related transformations with
mechanistic rationale: functionalisation of quinolones: a) X.
Zhang, Z. Qi and X. Li, Angew. Chem., Int. Ed., 2014, 53
8550-8551.
a
different 31 P. W. Davies, A. Cremonesi and N. Martin, Chem. Commun.,
2011, 47, 379-381.
,
32 See ref 24 for gold-catalysed double oxidation of triple bonds
using diphenylsulfoxide (3 equiv.) with AuCl/AgSbF6 (4
mol%), under reflux in 1,2-DCE.
10794-10798; b) U. Sharma, Y. Park and S. Chang, J. Org.
Chem., 2014, 79, 9899-9906; Formation of indolines: R. B.
Dateer and S. Chang, J. Am. Chem. Soc., 2015, 137, 4908- 33 For recent representative examples and overviews of gold
4911.
catalysed reactions of alkynes with other nucleophilic
oxidants see: a) L. Zhang, Acc. Chem. Res., 2014, 47, 877-888;
b) S. Bhunia, S. Ghorpade, D. B. Huple and R.-S. Liu, Angew.
Chem., Int. Ed., 2013, 52, 4229; c) S. Shi, T. Wang, W. Yang,
19 For similar overall transformations by hydrofunctionalisation
and then [3,3]-rearrangement see: a) S. Ngwerume and J. E.
Camp, Chem. Commun., 2011, 47
, 1857-1849; b) S.
Ngwerume, W. Lewis, and J. E. Camp, J. Org. Chem., 2013,
78, 920-934. For a stepwise variation using N-hydroxy
heterocycles see: c) M. Kumar, M. Scobie, M. S. Mashuta, G.
B. Hammond, and B. Xu Org. Lett., 2013, 15, 724-727; d) Y.
M. Rudolph and A. S. K. Hashmi, Chem. – Eur. J., 2013, 19,
6576–6580; d) J. Fu, H. Shang, Z. Wang, L. Chang, W. Shao, Z.
Yang and Y. Tang, Angew. Chem., Int. Ed., 2013, 52, 4198; e)
F. Pan, S. Liu, C. Shu, R.-K. Lin, Y.-F. Yu, J.-M. Zhou and L.-W.
Ye, Chem. Commun., 2014, 50, 10726–10729; f) G. Henrion,
T. E. J. Chavas, X. Le Goff and F. Gagosz, Angew. Chem., Int.
Ed., 2013, 52, 6277–6282.
Wang, L. Liu and L. Zhang, Chem. Sci., 2013, 4, 739-746; e) Y.
Wang, L. Ye and L. Zhang, Chem. Commun., 2011, 47, 7815-
7817; f) M. Kumar, M. Scobie, M. S. Mashuta, G. B.
Hammond and B. Xu, Org. Lett., 2013, 15, 724–727.
34 Oxidative cyclopropanation of enynes with pyridine-N-
oxides: a) D. Qian, H. Hu, F. Liu, B. Tang, W. Ye, Y. Wang, and
J. Zhang, Angew. Chem., Int. Ed., 2014, 53, 13751 –13755; b)
D. Vasu, H.-H. Hung, S. Bhunia, S. A. Gawade, A. Das, R.-S.
Liu, Angew. Chem., Int. Ed., 2011, 50, 6911-6914; c) K.-B.
20 In the course of preparing our work for publication, a report
appeared which includes one example of an acid catalysed
reaction of dibenzothiophene S-oxide with an ynamide to
provide a C-4 substituted dibenzothiophene: B. Peng, X.
Huang, L.-G. Xie, and N. Maulide, Angew. Chem. Int. Ed.,
2014, 53, 8718-8721.
Wang, R.-Q. Ran, S.-D. Xiu and C.-Y. Li, Org. Lett., 2013, 15
,
,
,
2374-2377; d) K. Ji and L. Zhang, Org. Chem. Front., 2014,
1
21 a) A. Fürstner and P. W. Davies, Angew. Chem., Int. Ed., 2007,
46, 3410-3439; b) D. J. Gorin and F. D. Toste, Nature, 2007,
34-38; e) D. Qian and J. Zhang, Chem. Commun., 2011, 47
11152-11154.
446, 395-403; c) J. Xiao and X. Li, Angew. Chem., Int. Ed., 35 The use of urea hydrogen peroxide afforded the sulfone
2011, 50, 7226–7236; d) M. Rudolph, A. Stephen and A. S. K.
preferentially and sodium metaperiodate gave no reaction.
Hashmi, Chem. Soc. Rev., 2012, 41, 2448–2462; e) L.-P. Liu 36 P. W. Davies, C. Detty-Mambo, Org. Biomol. Chem., 2010,
8
,
and G. B. Hammond, Chem. Soc. Rev., 2012, 41, 3129–3139;
f) A. S. K. Hashmi, Acc. Chem. Res., 2014, 47, 864–876; g) D.
Qian and J. Zhang, Chem. Rec., 2014, 14, 280–302; h) J. Xie,
2918-2922.
C. Pan, A. Abdukader and C. Zhu, Chem. Soc. Rev., 2014, 43
,
5245–5256; i) R. Dorel and A. M. Echavarren, Chem. Rev.,
2015, DOI: 10.1021/cr500691k.
22 a) P. W. Davies and S. J. C. Albrecht, Angew. Chem., Int. Ed.,
2009, 48, 8372−8375; b) P. W. Davies, Pure Appl. Chem.,
2010, 82, 1537−1544.
23 For a platinum-catalysed oxyarylation with nitrones, see: S.
Bhunia, C-J. Chang and R-S Liu, Org. Lett., 2012, 14, 5522–
5525.
24 C.-F Xu, M. Xu, Y.-X Jia and C. Li, Org. Lett., 2011, 13, 1556-
1559.
25 For gold-catalysed reactions where diphenylsulfoxide acts as
an oxidant following cyclisation of a gold-alkyne complex
see: a) C. A. Witham, P. Mauleón, N. D. Shapiro, B. D. Sherry
and F. D. Toste, J. Am. Chem. Soc., 2007, 129, 5838-5839; b)
H-S. Yeom and S. Shin, Org. Biomol. Chem., 2013, 11, 1089-
1092.
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Organic & Biomolecular Chemistry
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Journal Name
Graphical Abstract
ARTICLE
View Article Online
DOI: 10.1039/C5OB01241D
Site-selective and direct C-H functionalisation of
dibenzothiophenes is achieved using
oxyarylation approach.
a
gold-catalysed
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