Copper-Silver Dual Catalyzed Decyanative C–Se Cross-Coupling

Article abstract of DOI:10.1002/adsc.201600933

Traditionally, a metal-catalyzed cross-coupling reaction is governed by displacement of leaving groups such as halogens, tosylates, etc. by different nucleophiles leading to the formation of carbon-carbon and carbon-heteroatom bonds. Besides displacement of traditional leaving groups in coupling reactions decyanative cross-coupling has also received current attention. The objective of this work is to develop a decyanative cross-coupling through metal-assisted nucleophilic displacement, which is less explored so far. Thus, a decyanative cross-coupling of aryl selenocyanate with aryl-/alkylacetylenes, boronic acids and silanes has been accomplished by a copper-assisted nucleophilic displacement reaction for an easy access to a series of diaryl, aryl alkyl, aryl vinyl and aryl alkynyl selenides. The best yield of product was obtained using 5 mol% of Cu(OAc)₂, Ag₂CO₃(20 mol%) and Cs₂CO₃(1 equiv.) at 100 °C for 8 h in N-methylpyrrolidinone (NMP). The advantages of simple operation, high yields and general applicability make this procedure more attractive. A mechanistic pathway has been proposed. Silver plays a key role in the decyanation process. A plausible mechanistic pathway of this decyanative carbon-selenium cross-coupling has been proposed based on UV, EPR, HR-MS and IR analytical data along with results obtained from control experiments. (Figure presented.).

Full text of DOI:10.1002/adsc.201600933

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DOI: 10.1002/adsc.201600933
Copper-Silver Dual Catalyzed Decyanative C–Se Cross-Coupling
Nirmalya Mukherjee,a Debasish Kundu,a and Brindaban C. Ranua,*
a
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata – 700032, India
Fax : (+91)-33-2473-2805; phone: (+91)-33-2473-4971 ext. 1404; e-mail: ocbcr@iacs.res.in
Received: August 23, 2016; Revised: October 31, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600933.
Abstract: Traditionally, a metal-catalyzed cross-cou- vinyl and aryl alkynyl selenides. The best yield of
pling reaction is governed by displacement of leaving product was obtained using 5 mol% of Cu(OAc)2,
groups such as halogens, tosylates, etc. by different Ag2CO3 (20 mol%) and Cs2CO3 (1 equiv.) at 1008C
nucleophiles leading to the formation of carbon- for 8 h in N-methylpyrrolidinone (NMP). The advan-
carbon and carbon-heteroatom bonds. Besides dis- tages of simple operation, high yields and general ap-
placement of traditional leaving groups in coupling plicability make this procedure more attractive. A
reactions decyanative cross-coupling has also re- mechanistic pathway has been proposed. Silver plays
ceived current attention. The objective of this work a key role in the decyanation process. A plausible
is to develop a decyanative cross-coupling through mechanistic pathway of this decyanative carbon-sele-
metal-assisted nucleophilic displacement, which is nium cross-coupling has been proposed based on
less explored so far. Thus, a decyanative cross-cou- UV, EPR, HR-MS and IR analytical data along with
pling of aryl selenocyanate with aryl-/alkylacetylenes, results obtained from control experiments.
boronic acids and silanes has been accomplished by
a copper-assisted nucleophilic displacement reaction Keywords: copper; C–Se coupling; decyanation; or-
for an easy access to a series of diaryl, aryl alkyl, aryl ganoselenides; silver
Introduction
and natural products.[3] The C–Se bond formation is
widely accomplished involving ArSeSeAr via nucleo-
Carbon-heteroatom bond formation through cross- philic addition of ArSe to aryl halides,[4] aryldiazoni-
coupling reaction has emerged as powerful tool in or- um salts,[5] arylboronic acids,[6] and aryl alkynyl sele-
ganic synthesis and has found wide applications for nides[7] by Cu-assisted nucleophilic displacement of
the synthesis of biologically active molecules, scaf- halide moieties from C(sp2) and C(sp) centers. Re-
folds, drugs and natural products. In recent years the cently we have employed a heterogeneous alumina-
metal-assisted nucleophilic displacement protocol has supported Cu(II) catalyst for the synthesis of diaryl
provided an attractive alternative to the oxidative ad- and aryl heteroaryl selenides replacing the Br moiety
dition-reductive elimination pathway in transition in PhSeBr by this route.[8] The objective of the present
metal-catalyzed cross-coupling reactions as it excludes work is to develop a hitherto less explored decyana-
the uses of ligands which are required to maintain the tive cross-coupling through metal-assisted nucleophil-
proper bite angle in the active site of the metal or ic displacement. Thus we report a non-conventional
special forms of metal catalysts (e.g., nanoparticles).[1] cross-coupling of selenocyanate with acetylenes/bor-
This type of metal catalysis has been utilized involv- onic acids/silanes involving a Cu-Ag system for the
ing displacement of leaving groups such as halogens, synthesis
tosylates, etc. by different nucleophiles leading to the (Scheme 1).
formation of carbon-carbon and carbon-heteroatom
bonds.
of
functionalized
organoselenides
Besides displacement of traditional leaving groups Results and Discussion
in coupling reactions, decyanative cross-coupling has
received current attention.[2] On the other hand, phe- To optimize the reaction conditions a series of experi-
nylselenation is a useful process in organic synthesis ments was carried out with variation of catalyst, addi-
as organoselenides are of much importance due to tive, base, temperature, time and solvent for a repre-
their presence in several biologically active molecules sentative reaction of phenyl selenocyanate (1 equiv.)
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Scheme 1. Decyanative carbon-selenium cross-coupling.
and phenylacetylene (1 equiv.). An initial reaction 8) and Ag2CO3 was investigated and it was found that
using 5 mol% of Cu(OAc)2 and AgOAc (20 mol%) in the best yield of product was obtained using 5 mol%
the presence of Cs2CO3 (1 equiv.) in NMP (N-methyl- of Cu(OAc)2, Ag2CO3 (20 mol%) and Cs2CO3
pyrrolidinone) at 1008C under argon (Table 1, (1 equiv.) at 1008C for 8 h in NMP (Table 1, entry 9).
entry 1) led to 47% of the corresponding product Increase of catalyst loading (10 mol% of Cu catalyst)
(3aa). The change of base from Cs2CO3 to K2CO3 de- did not improve the yield (Table 1, entry 10). It has
creased the yield (Table 1, entry 2). The use of other been found that lowering of the amount of silver salt
copper salts such as CuO, CuSO4 and CuI did not pro- decreases the yield (Table 1, entry 11). Notably, the
duce better results than Cu(OAc)2 (Table 1, entries 3– copper or silver salt alone cannot drive the reaction
5). The combination of Cu(OAc)2 and other silver efficiently and, in the absence of both, the reaction
salts such as AgF, AgNO3, AgOTf (Table 1, entry 6– was not initiated (Table 1, entries 12–14). When the
Table 1. Optimization of the reaction conditions.[a]
Entry
Catalyst
Additive
Base
Temp. [oC]
Solvent
Yield [%][b]
1
2
3
4
5
6
7
8
Cu(OAc)2
Cu(OAc)2
CuO
CuSO4
CuI
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
–
AgOAc
AgOAc
AgOAc
AgOAc
AgOAc
AgF
AgNO3
AgOTf
Ag2CO3
Ag2CO3
Ag2CO3
–
Cs2CO3
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
–
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
120
50
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
DMF
DMSO
PhMe
NMP
NMP
47
38
38
23
18
34
28
38
93
93
42
31[e]
trace
–
47
93
42
62
64
44
92
52
9
10[c]
11[d]
12
13
14
15[f]
16
17
18
19
20
21[g]
22[h]
Ag2CO3
–
–
–
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Cu(OAc)2
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
100
100
100
100
100
[a]
Reaction conditions: phenyl selenocyanate (1.0 mmol) and phenylacetylene (1.0 mmol), Cu(OAc)2 (5 mol%), Ag salt
(20 mol%), Cs2CO3 (1 equiv.), 1008C, argon atmosphere, 8 h.
Yields of isolated pure products.
10 mol% of Cu catalyst.
10 mol% of Ag salt.
Along with the formation of diaryl diselenide (43%).
Cs2CO3 (0.5 equiv.).
[b]
[c]
[d]
[e]
[f]
[g]
[h]
For 10 h.
For 6 h.
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reaction is allowed to continue for a longer time (Table 2). Terminal alkynes containing electron-do-
(24 h) at higher temperature (1508C), no improve- nating groups like OMe, NMe2, 4-pentyl (Table 2, 3aj,
ment in the yield of desired product was observed in 3ab, and 3ac) underwent clean reactions by this pro-
case of both Cu catalysis and Ag catalysis alone. In- cedure. A similar efficiency was also observed with
creasing the amount of Cu (upto 25 mol%) does not electron-withdrawing groups and halo-substituted ter-
improve the product yield. The use of less Cs2CO3 de- minal alkynes like OCF3, CF3, F (Table 2, 3ah, 3ai,
creased the yield considerably (Table 1, entry 15). The and 3ae). The biphenyl- and phenoxy-substituted ter-
variation of temperature from 120 to 508C under oth- minal alkynes also led to the corresponding products
erwise identical reaction conditions established 1008C with good yield (Table 2, 3al and 3an). Polynuclear
as the optimum one (Table 1, entries 16 and 17). The arenes such as anthracene and naphthalene substitut-
use of other solvents like DMF, DMSO and toluene ed alkynes were also compatible for this reaction
did not lead to better results and thus NMP was (Table 2, 3ap and 3aj). Significantly, the aliphatic ter-
found to be the best choice (Table 1, entries 18–20). minal alkynes, ethyl propiolate and ethynylcyclohex-
The increase of reaction time (10 h) did not improve ane underwent selenylation with good yields (Table 2,
the yield and on the other hand reducing it to 6 h de- 3ag and 3ak). Earlier, in a similar reaction ethyl pro-
creased the yield (Table 1, entries 21 and 22).
piolate was reported to give a low yield (37%)[2c]
Thus, in a general experimental procedure a mixture whereas this protocol provided a 77% yield demon-
of phenyl selenocyanate (0.5 mmol), terminal alkyne strating its distinction to others. The di-substituted
(0.5 mmol) and Cu(OAC)2 (5 mol%) in NMP was product was obtained cleanly by the reaction of 1,3-
heated at 1008C under an argon atmosphere in the diethynylbenzene and phenyl selenocyanate (Table 2,
presence of Ag2CO3 (20 mol%) and Cs2CO3 3ad). The reaction with a heterocyclic alkyne also
(0.5 mmol) for a certain period of time to complete proceeded without any difficulty (Table 2, 3am, 3aq).
the reaction (TLC). A variety of diverse terminal al- The ferrocene-substituted alkyne was compatible for
kynes underwent reactions with phenyl selenocyanate this reaction too (Table 2, 3af). The fluorophenyl, het-
to produce the corresponding cross-coupled products eroaryl and ferrocene alkynyl selenides may poten-
Table 2. Phenylselenylation of terminal alkynes.[a]
[a]
Reaction conditions: aryl selenocyanate (0.5 mmol), terminal alkyne (0.5 mmol), Cu(OAc)2 (5 mol%), Ag salt (20 mol%),
Cs2CO3 (1 equiv.), NMP (3 mL), 1008C, 8–10 h, under an argon atmosphere.
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Table 3. Phenylselenylation of organoboronic acids.[a]
tially exhibit biological activity. Moreover, the func-
tionalized selenocyanate such as nitro-substituted aryl
selenocyanate was also successfully cross-coupled
with phenylacetylene to produce the corresponding
product (Table 2, 3ba) with moderate yield.
Interestingly, when 2-ethynylaniline was subjected
to this reaction the 2-substituted indole (4ar) was
formed exclusively via selenylation followed by base-
catalyzed cyclization (Scheme 2). This reaction may
be useful for the synthesis of substituted indoles
which are of potential value for biological activity.
Scheme 2. Phenylselenylation of 2-ethynylaniline.
Next, we investigated the reaction of boronic acids
or pinacol esters of boronic acids as an alternative
substrate. It was found that this catalytic system is
also successful for the formation of unsymmetrical or-
ganoselenides using boronic acids in place of terminal
alkynes (Table 3). The electron-donating (Me), elec-
tron-withdrawing (NO2, OCF3) substituted, fused ring
(naphthalene, acenaphthene) boronic acids and
hetero-nuclear (thiophene) boronic acids led to the
corresponding products in good yields (Table 3, 6aa,
6ab, 6ae, 6aj and 6ad). Increasing the steric bulk at
the reaction site decreases the product yield (Table 3,
6ac). The fused ring system like naphthalene also un-
derwent the reaction successfully to produce the cor-
responding selenylated product (Table 3, 6ag). Fur-
thermore, the reaction of vinylboronic acids went effi-
ciently under the reaction conditions to produce 1-
[a]
Reaction conditions: aryl selenocyanate (0.5 mmol), bor-
onic acid or its pinacol ester (0.5 mmol), Cu(OAc)2
(5 mol%), Ag salt (20 mol%), Cs2CO3 (1 equiv.), NMP
(3 mL), 1008C, 8–10 h, under an argon atmosphere.
methoxy-4-(2-phenylselanylvinyl)benzene
(Table 3,
6ah). The pinacol esters of boronic acids also under-
went clean reactions (Table 3, 6ai and 6af). Even the
electron-donating substituted aryl selenocyanates led
to the corresponding products in good yields (Table 3,
6ck, 6dk).
Scheme 3. Phenylselenylation of 4-acetylphenylboronic acid.
Interestingly, when 4-acetylphenylboronic acid was phenyl selenocyanate with ethynyltrimethylsilane pro-
subjected to this selenylation reaction the acetyl duced the unusual phenyl (phenylethynyl) selane
group was transformed to aldehyde in the presence of (Scheme 4, 3aa) by the cleavage of the aryl-selenium
1 equiv. of Ag2CO3. This is possibly due to the pres- bond[10] in phenyl selenocyanate.
ence of copper oxidant in the reaction medium[9]
(Scheme 3).
Next, we turned our attention to decarboxylative
decyanation which is unreported so far for the C–Se
The organosilanes also underwent selenylation bond formation. Thus we considered a reaction of
under the same reaction conditions (Scheme 4) to phenylpropiolic acid with phenyl selenocyanate in the
provide the corresponding selenylated products in presence of 1 equivalent of Ag2CO3 (optimized) and
good yield both in the case of aliphatic and arylsilane 5 mol% Cu(OAc)2 (Scheme 5). We observed that the
compounds (Scheme 4, 3aa and 8ab). The reaction of corresponding phenyl (phenylethynyl) selane 3aa was
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Scheme 6. Plausible radical mechanistic approach.
Scheme 4. Phenylselenylation of organosilanes.
coupling via a Cu(II)-assisted nucleophilic displace-
ment pathway.
As the Se–CN bond has a tendency to undergo
cleavage under heat to form selenium and cyano radi-
cals, we first considered the possibility of a radical
pathway for this reaction (Scheme 6),[12] where the ar-
ylseleno radical, generated from aryl selenocyanate,
may bind with Cu(II) center to form the Cu(III) inter-
mediate A. Then the arylboronic acid or arylacetylene
may interact with intermediate A to form intermedi-
ate B. Finally reductive elimination from B may lead
Scheme 5. Phenylselenylation of phenylpropiolic acid.
obtained in 74% yield likely through an Ag-assisted to the formation of the product.
decarboxylative[11]-decyanative process (see the Sup-
porting Information for further details).
However, the results of several control experiments
showed that the reaction rate and yield remained un-
In general, the reactions are clean and high yield- affected when the reaction was performed in the pres-
ing. All the reactions were performed in an inert at- ence of nitroarene (electron acceptor) or THF (elec-
mosphere since under open atmospheric conditions tron trapper) or TEMPO (radical quencher)
homolytic cleavage of the Se–CN bond occurs as (Scheme 7).[12] The EPR study indicated that Cu-re-
a competitive process and a significant amount of di- mained in the +2 oxidation state throughout the reac-
phenyl diselenide was obtained as by-product (30– tion (Figure 1a). Due to the presence of a high con-
35%) along with the desired product in low yield. centration of copper in the reaction medium initially
Under an inert atmosphere this oxidative side reac- a weak signal (due to antiferromagnetic spin ex-
tion was completely arrested and the yield of our de- change) was observed. But with the progress of the
sired product was significantly improved.
reaction, the intensity of the EPR signal of copper in-
A wide range of functionalized selenides was ob- creases indicating involvement of copper in the reac-
tained from terminal alkynes/organoboranes/organosi- tion medium.[13a] The EPR studies also revealed that
lanes by a general procedure using phenyl selenocya- no radical species was generated during the reaction,
nate. The reaction conditions are compatible with sev- even in the presence of TEMPO in the reaction
eral sensitive functionalities. This protocol has enor-
mous scope for an easy access to a library of organo-
selenides starting from any of the alkynes, boranes
and silanes. The compounds are obtained pure by
a simple column chromatography. The prepared com-
pounds were properly characterized by NMR, IR and
HR-MS analysis.
In order to gain insight into this C–Se bond forma-
tion through a decyanative pathway, a detailed mech-
anistic study has been undertaken. Two major possi-
bilities have been taken into consideration; (i) a radi-
cal mechanistic approach involving a Cu(III)-Cu(I)
reductive-elimination pathway and (ii) decyanative Scheme 7. Control experiments.
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Figure 1. (a) EPR scan of the reaction medium at a certain interval; (b) EPR scan of the reaction medium in the presence of
TEMPO at initial and final stages; (c) in-situ UV scan of the reaction medium at a certain interval.
medium (Figure 1b). No trace of diaryl diselenides Se–CN moiety via Cu(II)-assisted nucleophilic dis-
was observed as side product in this reaction via ter- placement to form B. Subsequently, Ag-promoted dis-
mination of arylseleno radicals. Thus, these experi- sociation of CN[13b] from B leads to C which provides
ments exclude the involvement of a radical process in the product with regeneration of Cu(II) for the next
this coupling.
cycle (Scheme 9).
Then we moved towards the other option of Cu-as-
sisted nucleophilic displacement pathway. To under-
stand whether the cyano moiety is present throughout
the reaction we have screened the reaction through
IR spectroscopic analysis and observed the presence
of the CN moiety until the completion of the reaction
as indicated by a characteristic peak near the
2200 cmÀ1 region. In addition, in a reaction between
phenylacetylene and PhSeCN in the presence of 4-
methoxyiodobenzene the formation of 4-methoxyben-
zonitrile (HR-MS, see the Supporting Information)
was observed along with the desired product
(Scheme 8). This experiment supported decyanative
coupling over the possibility of decarboxylation (CN
moieties have an inherent tendency to undergo car-
boxylation). Moreover the in situ UV experiment also
Scheme 9. Proposed mechanism for decyanative cross-cou-
pling.
supported the presence of Cu (II) centre (Figure 1c) Conclusions
throughout the reaction which was also suggested by
EPR analysis. These results clearly indicate that the In conclusion, we have introduced a decyanative
C–Se coupling proceeds through a Cu(II)-assisted nu- cross-coupling of aryl selenocyanate with aryl/alkyl
cleophilic displacement mechanism.
acetylenes, boronic acids and silanes by a copper-cata-
Thus, in the first step, acetylene or the aryl part of lyzed nucleophilic displacement reaction in the pres-
the boronic acid in the presence of a base interacts ence of silver providing a very efficient and general
with the Cu(II) center to form intermediate A[1,4b,7] protocol for the synthesis of unsymmetrical aryl aryl,
which then proceeds to react with the Ag(I)-activated aryl alkyl, aryl alkynyl, aryl heteroaryl and aryl ferro-
cynyl selenides which are of high potential in the
pharmaceutical chemistry. Aryl selenocyanate is a less
explored selenylating agent and the decyanative path
is quite new except for one earlier report.[2c] Thus this
reaction is of much significance. In addition, this pro-
tocol involves electrophilic substitution by PhSe+ in
milder nucleophiles such as arylalkynes, boranes and
silanes. The advantages of simple operation, high
yields and general applicability make this procedure
more attractive. Certainly this has much potential in
organic synthesis too. A plausible mechanism has
been proposed which provides a new dimension on
Scheme 8. Reaction between phenylacetylene and PhSeCN
in the presence of 4-methoxyiodobenzene.
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1,3-Bis[(phenylselanyl)ethynyl]benzene (Table 2, 3ad):
the reaction. Further applications of this new protocol
for the synthesis of related compounds are being pur-
sued.
Yellow liquid; IR (neat): n=3061, 3019, 2160, 1589, 1472,
1425, 1263, 1213 cmÀ1 1H NMR (500 MHz, CDCl3): d=
;
7.30–7.38 (m, 6H), 7.45–7.47 (m, 3H), 7.60–7.64 (m, 5H);
13C NMR (125 MHz, CDCl3): d=70.7, 102.0, 123.6, 127.3,
128.6, 128.7, 129.2, 129.3, 130.4, 131.6, 132.8, 134.6; anal.
calcd. for C22H14Se2: C 60.57, H 3.23; found: C 60.51, H
3.28%.
Experimental Section
[(3-Fluorophenyl)ethynyl](phenyl)selane[6] (Table 2, 3ae):
1H NMR (400 MHz, CDCl3): d=6.92–6.97 (m, 1H), 7.08–
7.10 (m, 1H), 7.16–7.27 (m, 5H), 7.49–7.50 (m, 2H);
13C NMR (100 MHz, CDCl3): d=71.1, 101.7 (d, J=4 Hz),
115.9 (d, J=79 Hz), 118.5 (d, J=23 Hz), 125.1 (d, J=9 Hz),
127.4–127.6 (m), 128.6, 129.4, 129.7, 130.0, 130.1, 162.5 (d,
J=245 Hz).
General Remarks
IR spectra were taken as KBr pellets for solids. NMR spec-
1
tra were recorded at 300, 400 and 500 MHz for H and 13C
spectra in CDCl3 solutions. Ag2CO3, AgNO3 and K2CO3 and
all acetylenes, boronic acids, organosilanes and phenyl sele-
nocyanate were procured commercially.
Ferrocene-ethynyl(phenyl)selane (Table 2, 3af): Reddish
brown oil; IR (neat): n=3061, 3019, 2160, 1589, 1472, 1425,
Representative Experimental Procedure for the
Cross-Coupling of Phenylacetylene and Phenyl
selenocyanate to Phenyl(phenylethynyl)selane[14a]
(Table 2, 3aa)
1
1263, 1213 cmÀ1; H NMR (500 MHz, CDCl3): d=4.23 (bs,
7H), 4.49 (s, 2H), 7.29 (d, J=8.5 Hz, 3H), 7.56 (d, J=
8.5 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=64.4, 64.9,
69.3, 69.4, 70.2, 70.3, 72.3, 76.8, 102.6, 127.0, 128.9, 129.6,
129.7; anal. calcd. for C18H14FeSe: C 59.21, H 3.86; found: C
59.19, H 3.89%.
In a 10-mL round-bottom flask a mixture of phenylacetylene
(51 mg, 0.5 mmol), phenyl selenocyanate (91 mg, 0.5 mmol),
Ag2CO3 (137 mg, 0.5 mmol), Cu(OAC)2 (9 mg, 0.05 mmol)
and NMP (3 mL) was heated at 1008C under argon for 8 h
(TLC). The reaction mixture was then allowed to cool and
was extracted with diethyl ether (3ꢁ20 mL). The extract
was washed with water (10 mL) and brine (10 mL). Then
the organic phase was dried over Na2SO4 and evaporated to
leave the crude product, which was purified by column chro-
matography over silica gel (hexane) to provide the pure
phenyl(phenylethynyl)selane as a yellow oil; yield: 120 mg
(93%). IR (neat): n=3016, 2978, 2845, 2158, 1679, 1588,
Ethyl 3-(phenylselanyl)propiolate[14b] (Table 2, 3ag):
1H NMR (500 MHz, CDCl3): d=1.31 (t, J=6.5 Hz, 3H),
4.25 (q, J=6.5 Hz, 2H), 7.30–7.36 (m, 3H), 7.55–7.56 (m,
2H); 13C NMR (100 MHz, CDCl3): d=14.2, 62.1, 74.9, 96.4,
126.2, 128.3, 130.0, 130.3, 152.7.
Phenyl{[4-(trifluoromethoxy)phenyl]ethynyl}selane
(Table 2, 3ah): Yellow liquid; IR (neat): n=3061, 3019,
1
2160, 1589, 1472, 1425, 1263, 1213 cmÀ1; H NMR (500 MHz,
CDCl3): d=7.18 (d, J=8 Hz, 2H), 7.26–7.36 (m, 3H), 7.50–
7.53 (m, 2H), 7.57–7.59 (m, 2H); 13C NMR (100 MHz,
CDCl3): d=70.8, 101.4, 119.5, 120.9, 121.5, 122.0, 127.4,
128.6, 129.3, 129.7, 133.3, 149.2; anal. calcd. for C15H9F3OSe:
C 52.80, H 2.66; found: C 52.85, H 2.69%.
1
1512, 1473 cmÀ1; H NMR (500 MHz, CDCl3): d=7.26–7.36
(m, 6H), 7.50–7.53 (m, 2H), 7.60–7.62 (m, 2H); 13C NMR
(125 MHz, CDCl3): d=69.4, 103.1, 123.3, 127.2, 128.5, 128.7,
129.0, 129.2, 129.7, 131.9 ppm; anal. calcd. for C14H10Se; C
65.38, H 3.92; found: C 65.42, H 3.87%.
Phenyl{[2-(trifluoromethyl)phenyl]ethynyl}selane
(Table 2, 3ai): Yellow oil; IR (neat): n=3061, 3019, 2160,
This procedure was followed for all the reactions listed in
Table 2, Table 3 as well as in Scheme 2, Scheme 3, Scheme 4
and Scheme 5. All of the unknown compounds are well
characterized by their spectroscopic and spectrometric data
(IR, 1H NMR, 13C NMR, HR-MS and elemental analysis)
and the known compounds were identified by comparison of
their spectroscopic data with those reported earlier. All
these data are provided below.
1589, 1472, 1425, 1263, 1213 cmÀ1
;
1H NMR (500 MHz,
CDCl3): d=7.28–7.42 (m, 4H), 7.45–7.54 (m, 1H), 7.61–7.62
(m, 4H); 13C NMR (100 MHz, CDCl3): d=76.5, 98.9, 121.8
(d, J=83 Hz), 125.0, 125.9 (t, J=5 Hz), 127.4, 127.7, 128.3
(d, J=47 Hz), 129.2–129.7 (m), 131.0–131.5 (m), 133.8; anal.
calcd. for C15H9F3Se: C 52.40, H 2.79; found: C 52.44, H
2.74%.
[(6-Methoxynaphthalen-2-yl)ethynyl](phenyl)selane[6]
N,N-Dimethyl-4-[(phenylselanyl)ethynyl]aniline (Table 2,
3ab): Brownish oil; IR (neat): n=3066, 3018, 2968, 2927,
2399, 2219, 1600, 1572, 1487, 1452, 1442, 1317, 1261,
1
(Table 2, 3aj): H NMR (500 MHz, CDCl3): d=3.83 (s, 3H),
7.02 (d, J=2.5 Hz, 1H), 7.07 (dd, J=9, 2.5 Hz, 1H), 7.17–
7.20 (m, 1H), 7.24–7.27 (m, 2H), 7.42 (dd, J=8.5, 1.5 Hz,
1H), 7.53–7.54 (m, 2H), 7.60 (t, J=8.5 Hz, 2H), 7.86 (s,
1H); 13C NMR (100 MHz, CDCl3): d=55.4, 68.7, 103.6,
106.0, 118.1, 119.6, 126.9, 127.2, 128.5, 129.1, 129.2, 129.3,
129.5, 129.7, 131.8, 134.4, 158.6.
1215 cmÀ1 1H NMR (500 MHz, CDCl3): d=2.90 (s, 6H),
;
6.55 (d, J=9 Hz, 2H), 7.14–7.16 (m, 1H), 7.22 (t, J=7.5 Hz,
2H), 7.32 (d, J=8.5 Hz, 2H), 7.48–7.50 (m, 2H); 13C NMR
(125 MHz, CDCl3): d 40.3, 65.8, 104.6, 111.8, 126.8, 128.7,
129.5, 130.0, 130.5, 132.9, 133.7, 150.6; anal. calcd. for
C16H15NSe: C 64.00, H 5.04, N 4.66; found: C 64.12, H 5.08,
N 4.59%.
(Cyclohexylethynyl)(phenyl)selane (Table 2, 3ak): Yellow
viscous liquid; IR (neat): n=2956, 2929, 2858, 2218, 1577,
1
1458, 1379 cmÀ1; H NMR (500 MHz, CDCl3): d=1.23–1.26
[(4-Pentylphenyl)ethynyl](phenyl)selane[6] (Table 2, 3ac):
1H NMR (500 MHz, CDCl3): d=0.90–0.95 (m, 3H), 1.29–
1.40 (m, 4H), 1.60–1.66 (m, 2H), 2.62 (t, J=8 Hz, 2H), 7.16
(d, J=8 Hz, 2H), 7.27 (t, J=6.5 Hz, 1H), 7.34 (t, J=8 Hz,
2H), 7.43–7.49 (m, 2H), 7.60 (d, J=7.5 Hz, 2H); 13C NMR
(125 MHz, CDCl3): d=14.1, 22.6, 31.0, 31.6, 36.0, 68.2,
103.3, 120.4, 127.1, 128.6, 129.0, 129.3, 129.6, 131.9, 144.0.
(m, 3H), 1.42–1.48 (m, 3H), 1.64–1.68 (m, 2H), 1.77–1.80
(m, 2H), 2.53–2.57 (m, 1H), 7.11–7.15 (m, 1H), 7.17–7.22
(m, 2H), 7.41–7.43 (m, 2H); 13C NMR (125 MHz, CDCl3):
d=24.9, 25.9, 31.0, 32.7, 57.5, 108.9, 126.6, 128.5, 129.4,
129.7; anal. calcd. for C14H16Se: C 63.88, H 6.13; found: C
63.81, H 6.18%.
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([1,1’-Biphenyl]-4-ylethynyl)(phenyl)selane[6]
(Table 2,
1H NMR (400 MHz, CDCl3): d=6.88 (d, J=1.2 Hz, 1H),
7.11–7.15 (m, 1H), 7.18–7.24 (m, 4H), 7.29–7.34 (m, 3H),
7.63 (d, J=8 Hz, 1H), 8.17 (bs, 1H); 13C NMR (125 MHz,
CDCl3): d=110.8, 112.6, 120.1, 120.3, 120.6, 123.1, 126.9,
128.9, 129.5, 130.3, 131.7, 138.3; anal. calcd. for C14H11NSe:
C 61.77, H 4.07, N 5.15; found: C 61.72, H 4.08, N 5.19%.
3al): 1H NMR (500 MHz, CDCl3): d=7.30 (t, J=7.5 Hz,
1H), 7.35–7.41 (m, 3H), 7.48 (t, J=7.5 Hz, 2H), 7.60–7.65
(m, 8H); 13C NMR (100 MHz, CDCl3): d=70.1, 102.9, 122.1,
127.1, 127.2, 127.8, 128.9, 129.1, 129.2, 129.7, 132.3, 140.3,
141.4.
Phenyl(o-tolyl)selane[14c]
(Table 3,
6aa):
1H NMR
2-[(Phenylselanyl)ethynyl]pyridine
Brownish liquid; IR (neat): n=3066, 3018, 2968, 2927, 2399,
2219, 1600, 1572, 1487, 1452, 1442, 1317, 1261, 1215 cmÀ1
(Table 2,
3am):
(400 MHz, CDCl3): d=2.44 (s, 3H), 7.10 (t, J=7.6 Hz, 1H),
7.21–7.26 (m, 5H), 7.39 (d, J=7.6 Hz, 1H), 7.43–7.45 (m,
2H); 13C NMR (100 MHz, CDCl3): d=22.4, 126.8, 127.2,
127.9, 129.4, 130.3, 130.9, 131.8, 132.8, 132.9, 133.8, 140.0.
;
1H NMR (500 MHz, CDCl3): d=7.12–7.14 (m, 1H), 7.17–
7.21 (m, 1H), 7.21–7.26 (m, 4H), 7.35 (d, J=8 Hz, 1H),
7.52–7.58 (m, 3H), 8.49 (d, J=4 Hz, 1H); 13C NMR
(100 MHz, CDCl3): d=71.7, 102.3 (d, J=3 Hz), 122.9, 126.9,
127.5, 128.0, 129.6, 129.7, 136.2, 143.1, 150.0; anal. calcd. for
C13H9NSe: C 60.48, H 3.51, N 5.43; found: C 60.44, H 3.58,
N 5.41%.
1
(3-Nitrophenyl)(phenyl)selane[4a] (Table 3, 6ab): H NMR
(400 MHz, CDCl3): d=7.34–7.40 (m, 4H), 7.57–7.59 (m,
2H), 7.64 (d, J=7.6 Hz, 1H), 8.04 (dd, J=7.6, 1.2 Hz, 1H),
8.20 (t, J=1.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=
121.7, 125.9, 128.6, 128.9, 129.4, 129.9, 130.0, 134.9, 137.0,
148.7.
[(4-Phenoxyphenyl)ethynyl](phenyl)selane (Table 2, 3an):
Yellow liquid; IR (neat): n=3061, 3019, 2160, 1589, 1472,
Mesityl(phenyl)selane[14d]
(Table 3,
6ac):
1H NMR
1
1425, 1263, 1213 cmÀ1; H NMR (500 MHz, CDCl3): d=6.95
(500 MHz, CDCl3): d=2.33 (s, 3H), 2.46 (s, 6H), 7.02 (s,
2H), 7.09–7.13 (m, 3H), 7.15–7.17 (m, 2H); 13C NMR
(100 MHz, CDCl3): d=21.1, 24.3, 125.5, 126.9, 128.6, 128.7,
128.9, 129.2, 133.6, 139.2, 143.7.
(dd, J=9, 2.5 Hz, 2H), 7.04 (d, J=8 Hz, 2H), 7.15 (t, J=
7.5 Hz, 1H), 7.25–7.28 (m, 1H), 7.32–7.39 (m, 4H), 7.46–
7.49 (m, 2H), 7.57–7.60 (m, 2H); 13C NMR (125 MHz,
CDCl3): d=68.4, 102.6, 117.8, 118.4, 119.6, 124.1, 127.2,
129.1, 129.2, 129.6, 130.0, 133.7, 156.4, 158.1; anal. calcd. for
C20H14OSe: C 68.77, H 4.04; found: C 68.71, H 4.08%.
[(3-Methoxyphenyl)ethynyl](phenyl)selane (Table 2, 3ao):
Yellow liquid; IR (neat): n=3061, 3019, 2160, 1589, 1472,
3-(Phenylselanyl)thiophene[14h] (Table 3, 6ad): 1H NMR
(500 MHz, CDCl3): d=7.09 (dd, J=5, 1 Hz, 1H), 7.17–7.27
(m, 3H), 7.31–7.45 (m, 3H); 13C NMR (125 MHz, CDCl3):
d=122.8, 126.8, 126.9, 129.2, 129.3, 131.1, 132.3, 132.8.
Phenyl[4-(trifluoromethoxy)phenyl]selane (Table 3, 6ae):
Colourless oil; IR (neat): n=3061, 3019, 2160, 1589, 1472,
1
1425, 1263, 1213 cmÀ1; H NMR (400 MHz, CDCl3): d=3.83
(s, 3H), 6.89 (d, J=8.4 Hz, 2H), 7.26–7.36 (m, 3H), 7.49 (d,
J=8.4 Hz, 2H), 7.61 (d, J=7.6 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=55.3, 67.3, 103.0, 114.0, 115.3, 127.0,
128.8, 128.9, 129.0, 129.3, 129.5, 133.6, 160.0; anal. calcd. for
C15H12OSe: C 62.73, H 4.21; found: C 62.79, H 4.28%.
(Phenanthren-9-ylethynyl)(phenyl)selane (Table 2, 3ap):
Yellow viscous liquid; IR (neat): n=2956, 2929, 2858, 2218,
1
1425, 1263, 1213 cmÀ1; H NMR (500 MHz, CDCl3): d=7.12
(d, J=9 Hz, 2H), 7.29–7.32 (m, 3H), 7.46 (dd, J=9, 1.5 Hz,
2H), 7.49–7.52 (m, 2H); 13C NMR (125 MHz, CDCl3): d=
121.6, 121.9, 128.0, 129.7, 130.0, 130.4, 133.6, 134.0, 134.1,
148.7; anal. calcd. for C13H9F3OSe: C 49.23, H 2.86; found:
C 49.21, H 2.91%.
Pent-1-yn-1-yl(phenyl)selane[14i] (Table 3, 6af): 1H NMR
(400 MHz, CDCl3): d=1.04 (t, J=7.2 Hz, 3H), 1.58–1.66
(m, 2H), 2.44 (t, J=7.2 Hz, 2H), 7.23–7.25 (m, 1H), 7.28–
7.32 (m, 2H), 7.52–7.54 (m, 2H); 13C NMR (125 MHz,
CDCl3): d=13.6, 22.3, 22.6, 57.7, 104.6, 126.8, 128.7, 129.4,
129.5.
1577, 1458, 1379 cmÀ1 1H NMR (500 MHz, CDCl3): d=
;
7.30–7.33 (m, 1H), 7.37–7.41 (m, 2H), 7.59–7.62 (m, 1H),
7.65–7.73 (m, 5H), 7.85 (d, J=8 Hz, 1H), 8.06 (s, 1H), 8.48–
8.50 (m, 1H), 8.64–8.69 (m, 2H); 13C NMR (100 MHz,
CDCl3): d=73.8, 101.4, 119.6, 122.7, 122.9, 127.0, 127.1,
127.2, 127.3, 127.4, 127.7, 128.7, 129.1, 129.3, 129.7, 130.2,
130.4, 130.5, 131.2, 131.3, 132.5; HR-MS: m/z=267.0648,
calcd. for C14H18Se (M+ +H): 267.0652.
1
Naphthalen-2-yl(phenyl)selane[3b] (Table 3, 6ag): H NMR
(300 MHz, CDCl3): d=7.27 (dd, J=6.3, 3.3 Hz, 3H), 7.44–
7.54 (m, 5H), 7.73 (d, J=7.8 Hz, 2H), 7.78–7.82 (m, 1H),
7.99 (s, 1H); 13C NMR (75 MHz, CDCl3): d=126.3, 126.6,
127.5, 127.9, 128.6, 128.9, 129.5, 130.6, 131.3, 132.2, 132.6,
133.0, 134.1.
3-[(Phenylselanyl)ethynyl]thiophene
(Table 2,
3aq):
White viscous liquid; IR (neat): n=2956, 2929, 2858, 2218,
1
1577, 1458, 1379 cmÀ1; H NMR (300 MHz, CDCl3): d=7.18
(dd, J=5.1, 0.9 Hz, 1H), 7.26–7.36 (m, 4H), 7.53–7.59 (m,
3H); 13C NMR (100 MHz, CDCl3): d=68.9, 97.9, 116.3,
122.4, 125.4, 127.2, 129.0, 129.2, 129.7, 129.9, 130.2; HR-MS:
m/z=264.9583, calcd. for C12H9SSe (M+ +H): 264.9585.
(2-Nitrophenyl)(phenylethynyl)selane (Table 2, 3ba): Pale
yellow liquid; IR (neat): n=3066, 3018, 2968, 2927, 2399,
(E)-(4-Methoxystyryl)(phenyl)selane[14e] (Table 3, 6ah):
1H NMR (300 MHz, CDCl3): d=3.81 (s, 3H), 6.85–7.05 (m,
4H), 7.25–7.31 (m, 5H), 7.52–7.55 (m, 2H); 13C NMR
(75 MHz, CDCl3): d=55.4, 114.2, 116.0, 127.2, 127.5, 129.4,
130.0, 130.9, 132.1, 136.0, 159.5.
(3-Methoxyprop-1-yn-1-yl)(phenyl)selane[14g]
(Table 3,
2219, 1600, 1572, 1487, 1452, 1442, 1317, 1261, 1215 cmÀ1
;
1
1H NMR (500 MHz, CDCl3): d=7.35–7.40 (m, 3H), 7.43 (t,
J=8 Hz, 1H), 7.55–7.57 (m, 2H), 7.62–7.66 (m, 1H), 8.32–
8.37 (m, 2H); 13C NMR (100 MHz, CDCl3): d=71.9, 76.8,
106.6, 122.7, 126.3, 127.2, 128.6, 129.3, 130.9, 132.1, 134.7,
145.2; anal. calcd. for C14H9NO2Se: C 55.64, H 3.00, N 4.64;
found: C 55.69, H 3.08, N 4.59%.
6ai): H NMR (500 MHz, CDCl3): d=3.42 (s, 3H), 4.31 (s,
2H), 7.26 (t, J=7.5 Hz, 1H), 7.31 (t, J=10 Hz, 2H), 7.53 (d,
J=8 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=57.7, 61.0,
67.0, 99.9, 127.3, 129.3, 129.6, 132.9.
(1,2-Dihydroacenaphthylen-5-yl)(phenyl)selane[14i]
(Table 3, 6aj): 1H NMR (400 MHz, CDCl3): d=3.25–3.33
(m, 4H), 7.05–7.08 (m, 3H), 7.13–7.16 (m, 1H), 7.19 (dd,
J1 =1.2 Hz, J2 =12 Hz, 3H), 7.35–7.44 (m, 1H), 7.76 (dd,
J1 =5.6 Hz, J2 =24 Hz, 2H); 13NMR (100 MHz, CDCl3): d=
2-(Phenylselanyl)-1H-indole (Scheme 2, 4ar): Off-white
viscous oil; IR (neat): n=3066, 3018, 2968, 2927, 2399, 2219,
1600, 1572, 1487, 1452, 1442, 1317, 1261, 1215 cmÀ1
;
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30.2, 30.6, 120.0, 122.7, 122.9, 126.3, 128.9, 129.2, 130.6,
132.9, 133.5, 136.9, 140.0, 146.5, 148.2.
Med. Chem. 1995, 3, 1255–1262; g) J. M. Bernardon, P.
Diaz, PCT Int. Appl. WO 9965872A1 19991223, 1999;
h) C. Millois, P. Diaz, Org. Lett. 2000, 2, 1705–1708.
[4] For C–Se bond formation using aryl halides, see: a) K.
Swapna, S. N. Murthy, Y. V. D. Nageswar, Eur. J. Org.
Chem. 2011, 1940–1946; b) T. Chatterjee, B. C. Ranu, J.
Org. Chem. 2013, 78, 7145–7153; c) M. Tobisu, Y.
Masuya, K. Baba, N. Chatani, Chem. Sci. 2016, 7, 2587–
2591; d) V. P. Reddy, A. V. Kumar, K. Swapna, K. R.
Rao, Org. Lett. 2009, 11, 951–953; e) Y. Li, H. Wang,
X. Li, T. Chen, D. Zhao, Tetrahedron 2010, 66, 8583–
8586; f) W. Xie, B. Li, B. Wang, J. Org. Chem. 2016, 81,
396–403.
[5] For C–Se bond formation starting from aryldiazonium
salts or anilines, see: a) D. Kundu, S. Ahammed, B. C.
Ranu, Green Chem. 2012, 14, 2024–2030; b) N. Mukher-
jee, T. Chatterjee, B. C. Ranu, J. Org. Chem. 2013, 78,
11110–11114; c) D. Kundu, S. Ahammed, B. C. Ranu,
Org. Lett. 2014, 16, 1814–1817.
[6] For C–Se bond formation using arylboronic acids, see:
a) L. Wang, M. Wang, F. Huang, Synlett 2005, 13, 2007–
2010; b) N. Taniguchi, Synlett 2006, 1351–1354; c) N.
Taniguchi, J. Org. Chem. 2007, 72, 1241–1245; d) D.
Alves, C. G. Santos, M. W. Paix¼o, L. C. Soares, D. d.
Souza, O. E. D. Rodrigues, A. L. Braga, Tetrahedron
Lett. 2009, 50, 6635–6638; e) M. Wang, K. Ren, L.
Wang, Adv. Synth. Catal. 2009, 351, 1586–1594; f) V. G.
Ricordi, C. S. Freitas, G. Perin, E. J. Lenard¼o, R. G.
Jacob, L. Savegnago, D. Alves, Green Chem. 2012, 14,
1030–1034; g) B. Zheng, Y. Gong, H.-J. Xu, Tetrahe-
dron 2013, 69, 5342–5347; h) A. Kumar, S. Kumar, Tet-
rahedron 2014, 70, 1763–1772; i) S. Roy, T. Chatterjee,
B. Banerjee, N. Salam, A. Bhaumik, S. M. Islam, RSC
Adv. 2014, 4, 46075–46083; j) H. Zhao, Y. Jiang, Q.
Chen, M. Cai, New J. Chem. 2015, 39, 2106–2115; k) B.
Mohan, C. Yoon, S. Jang, K. H. Park, ChemCatChem
2015, 7, 405–412; l) S. Roy, T. Chatterjee, S. M. Islam,
Tetrahedron Lett. 2015, 56, 779–783, and also the refer-
ences cited therein.
4-(Phenylselanyl)benzaldehyde[3b]
(Scheme 3,
6ak):
1H NMR (500 MHz, CDCl3): d=7.35–7.40 (m, 5H), 7.60 (d,
J=8.5 Hz, 2H), 7.67 (d, J=10 Hz, 2H), 9.90 (s, 1H);
13C NMR (100 MHz, CDCl3): d=128.1, 129.0, 130.0, 130.2,
130.3, 134.6, 135.6, 142.8, 191.5.
Phenyl(o-tolyl)selane[5f] (Table3, 6ck): Yellow liquid;
1H NMR (500 MHz, CDCl3): d=2.46 (s, 3H), 7.10–7.13 (m,
1H), 7.23–7.39 (m, 5H), 7.40–7.46 (m, 1H); 13C NMR
(100 MHz, CDCl3): d=22.4, 126.8, 127.2, 127.9, 129.4, 130.3,
130.9, 131.8, 132.8, 133.8, 140.0.
(3-Isopropoxyphenyl)(phenyl)selane
(Table 3,
6dk):
Yellow gummy liquid; IR (neat): n=3140, 2976, 2935, 2851,
1718, 1585, 1480, 1440, 1378, 1276, 1245, 1171, 1120, 1017,
1
946 cmÀ1; H NMR (500 MHz, CDCl3): d=1.34 (d, J=6 Hz,
6H), 4.54 (m, 1H), 6.83 (dd, J1 =2 Hz, J2 =6.5 Hz, 2H),
7.19–7.22 (m, 3H), 7.33–7.35 (m, 2H), 7.48 (dd, J=2 Hz, J=
6.5 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=22.0, 22.1,
70.1, 76.85, 117.0, 119.7, 126.5, 129.27, 131.1, 133.39, 136.6,
138.3, 158.3; anal. calcd. for C15H16OSe: C 61.86, H 5.5;
found: C 61.69, H 5.68%.
Diphenylselane[3b] (Scheme 4, 8ab): 1H NMR (500 MHz,
CDCl3): d=7.25–7.31 (m, 6H), 7.62–7.65 (m, 4H); 13C NMR
(100 MHz, CDCl3): d=127.8, 129.3, 131.0, 131.7.
Acknowledgements
We gratefully acknowledge financial support from DST,
Govt. of India, New Delhi (Grant no. SR/S2/JCB-11/2008)
for the award of a J. C. Bose fellowship to B.C.R. and Indian
National Science Academy, New Delhi for the offer of INSA
Sr. Scientist position to B.C.R. N.M. and D.K. thank DST for
their Fellowships.
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Copper-Silver Dual Catalyzed Decyanative C–Se Cross-
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