Visible-light-induced phenylchalcogenyl-oxygenation of allenes having aryl or electron withdrawing substituents with ambient air as a sole oxidant

Article abstract of DOI:10.1039/c6ob02033j

The synthesis of regio- and stereoselective aryl substituted α,β-unsaturated aldehydes and ketones from activated allenes was achieved. This mild and non-metallic oxidation is exclusively driven by benign ambient air and triggered by visible light. The same starting materials under ideal anaerobic conditions led to the 2,3-diphenylselenation adduct with no trace of oxygenated products, demonstrating dissolved oxygen as a chemical switch for two different reaction pathways. The salient feature of this protocol is the single electron transfer (SET) achieved by irradiation of one of two organic molecules thereby avoiding a sensitizer to form a radical ion pair.

Full text of DOI:10.1039/c6ob02033j

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Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C6OB02033J
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ARTICLE
Visible-Light-Induced Phenylchalcogenyl-Oxygenation of Allenes
Having Aryl- / or Electron Withdrawing Substituent with Ambient
Air as Sole Oxidant
Gullapalli Kumaraswamy,*a,b Swargam Vijaykumar,a Kukkadapu Ankammaa and Vykunthapu
Received 00th January 20xx,
Accepted 00th January 20xx
Narayanaraoa
DOI: 10.1039/x0xx00000x
Abstract. Synthesis of regio- and stereoselective aryl substituted ,-unsaturated aldehydes and ketones from activated
allenes was achieved. This mild and non-metallic oxidation is exclusively driven by benign ambient air triggered by visible
light. The same starting materials under ideal anaerobic conditions led to the 2, 3-diphenyselenation adduct with no trace
of oxygenated product, demonstrating dissolved oxygen as chemical switch for two different reaction pathways. The
salient feature of this protocol is the single electron transfer (SET) achieved by irradiation of one of two organic molecules
thereby avoiding a sensitizer to form a radical ion pair and the side product PhSeOH generated during reaction is oxidized
under the reaction conditions to starting material PhSeSePh.
www.rsc.org/
ion pair. This radical ion pair is disproportionated and then
undergoes element-element addition to an unsaturated
carbon-carbon bond in analogy with an earlier report (Scheme
Introduction
Research on visible-light-induced photo-redox catalysis has
developed rapidly in recent years, such that this type of
catalysis has become a reliable synthetic method in the area of
carbon-carbon and carbon-heteroatom bond formation.1 The
activation of organic molecules by means of visible-light is
considered as a sustainable, energetically favorable benign
route that complies with the principles of green chemistry. Of
late, the photo-induced single electron transfer (PET)
1, (c)).4
Previous work:
h
SePh
SePh
•
tungsten lamp (500 W)
+
PhSeSePh
CDCl3, 15 C
2a
1h
1a
3aa
Ref: 4a
(E/Z = 33/67, 78%yield)
activation mode has bestowed
a manifold of practical
procedures for the construction of organic molecules.2
Recently, a diverse range of photocatalytic transformations
with unconventional reactivity have emerged, and this
scenario unlocks the opportunity to explore classical radical
chemistry with reference to visible-light induced photo-redox
catalysis.3 Considering the organic transformations enabled by
photo-redox catalysis, we initiated a program for the synthesis
of functionalized organic compounds by means of the direct
addition of two different heteroatom groups into carbon-
carbon unsaturated bonds.
This work:
R2
O
h
White LEDs
R2
PhXXPh (0.6 equiv)
XPh
•
LiCl (1.0 equiv)
MeCN
H
R1
R1
X = Se, Te
70-92% yields
Z:E = 9:1 or 8:2
rt, 3-6 h
(1.0 equiv)
ambient air
R1 = alkyl, alkoxy, halo
R2 = H, Me
At the outset, we considered studying the effect of the single
electron transfer (SET) phenomenon from diphenyl diselenide
(PhSeSePh, 2a) and 3-phenylpropa-1,2-diene 1a under visible-
light irradiation, anticipating the generation of an active radical
Scheme 1. Prior art synthesis of the diselenation adduct and arylchalcogenyl ,-
unsaturated aldehydes and ketones.
The reactivity of the photo-induced SET generated radical ions
could be controlled by the solvent polarity.5 Consequently, we
hypothesized that solvent-separated ions in a polar aprotic
a.CSIR-Indian Institute of Chemical Technology, Hyderabad-500 607, Telangana,
India
E-mail: gkswamy_iict@yahoo.co.in
solvent such as acetonitrile (dielectric constant
 at 25 °C =
36.64, oxygen solubility 8.1 mM / cm3)6 could be intercepted
by dioxygen via selective radical coupling. Eventually, the
peroxy intermediate would dismutate, then would likely
deliver chalcogenyl-oxygenated compounds.
Tel: + 91-40-27193154. Fax: + 91-40-27193275.
b.Academy of Scientific and Innovative Research (AcSIR), New Delhi 110 025, India.
† Electronic Supplementary Information (ESI) available: Copies of 1H and 13C NMR
spectra’s free of charge via Internet. See DOI: 10.1039/x0xx00000x
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To confirm the source of aldehyde oxygen, we VpieewrfAortircmle Oednlinae
photoreaction with deaerated, anhydrDoOusI: 10a.c1e0t3o9/nCit6rOilBe02i0n33aJ
completely inert atmosphere under conditions otherwise
identical to those above. As expected, 1,2-diphenylselenation
of the terminal double bond produced 3aa as a Z:E mixture at
a yield of 45%4a with a trace of 3a (Table 1, entry 2). This result
indicates that the aldehyde oxygen originates from molecular
oxygen. Next, we became interested in performing the same
reaction with anhydrous acetonitrile in open air. The desired
product 3a was obtained in 65% yield (Table 1, entry 3).
Further, a significant increase in the yield of 3a (85%) was
found using 1 equivalent of LiCl (Table 1, entry 4).10 Other salts
such as LiI and NaCl gave inferior yields, whereas 2 equivalents
of LiCl did not improve the yield of 3a (Table 1, entries 5, 6 and
7). In the solvent screening step, halogenated, aprotic and
protic solvents were assessed. Acetonitrile was found to be
useful solvent for this transformation (Table 1, entries 8, 9, 10
and 11). Experimentation with the molar ratio of PhSeSePh
indicated that 0.6 equivalent of 2a is sufficient to complete the
reaction. The 23W CFL illumination also promoted the reaction
with equal efficiency (Table 1, entry 12). No reaction occurred
Results and Discussion
Initially, a reaction was carried out with 3-phenyl propa-1,2-
diene 1a7 (1.0 mmol, 1.0 equiv) and PhSeSePh8 2a (1.1 mmol,
1.1 equiv) in acetonitrile while stirring at ambient temperature
and under irradiation with a household 7 W Day light-white
LED lamp (λmax = 430-730 nm) using an oxygen balloon. After 3
h, the sole product obtained in 45% yield was analyzed to be
2,3-adduct 3a as a major isomer along with the minor E
isomer. The Z:E mixture was separated by silica gel column
chromatography, and the diastereoselectivity (9:1) was
determined from the isolated individual weights of the Z:E
isomers (Table 1, entry 1).9 This was in contrast to previous
reports wherein visible-light irradiation gave diselenation
adduct 3aa (Scheme 1 (c)) with an 8:2 ratio of the Z:E mixture
as a sole product,4 with no trace of formylated product 3a
observed.
Table 1. Optimization studies of the -phenylselenyl-oxygenation of 1a and 2a
with visible-light irradiationa
H
H
O
•
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h
in the absence of light, and heating at 45 C also failed to give
XPh
the 3a (Table 1, entries 13 and 14). As expected, the visible-
light promoted reaction between diphenyl ditelluride 2b and
1a under standard conditions proceeded effectively, and the
expected product 3ab was isolated as a 9:1 mixture in 90%
yield (Table 1, entry 15).4a In sharp contrast, the reaction of
diphenyldisulfide 2c with 1a under similar conditions did not
occur, and only the starting materials were recovered (Table 1,
entry 16).
2a-c (0.6 equiv)
1a (1.0 equiv)
LiCl (1.0 equiv)
+
3a, X = Se,
86% yield
3ab, X = Te,
Z:E = 9:1
MeCN
rt, open air, 6 h
PhXXPh (0.6 equiv)
2a, X = Se
2b, X = Te
2c, X = S
Z:E = 9:1
90% yield, (Z:E mixture)
3ac, X = S,
No reaction
Entry
2 (equiv)
Solvent
Additive
% yieldb
1
1.1
MeCN
3a, 45c
2
3
1.1
1.1
MeCN
MeCN
3aa, 45d
3a, 65
Table 2. Scope of the reaction with respect to aryl allenesa
4
5
6
1.1
1.1
1.1
MeCN
MeCN
MeCN
LiCl (1.0 equiv)
LiI (1.0 equiv)
NaCl (1.0 equiv)
3a, 85
3a, 40
3a, 30
h White LEDs
2a (0.6 equiv)
H
O
•
MeCN, rt
open air, 6 h
Ar
7
1.1
MeCN
LiCl (2.0 equiv)
3a, 86
Ar
SePh
1b-n
3b-n
8
1.1
1,4-
LiCl (1.0 equiv)
NR
dioxane
Entry
Ar (1b-n)
Product (3b-n) (Z:E ratio),
% Yield of Major Z isomer
3b (9:1), 86
9
10
1.1
1.1
DMF
MeOH
LiCl (1.0 equiv)
LiCl (1.0 equiv)
NR
3a, 80
1
2
3
4
5
6
7
8
9
10
11
12
13
1b, Ar = (4-Me-C6H4)
1c, Ar = (4-t-Bu-C6H4)
1d, Ar = (2,4,5-Me-C6H2)
1e, Ar = (4-MeO-C6H4)
1f, Ar = (3,5-MeO-C6H3)
1g, Ar = (4-F-C6H4)
1h, Ar = (3,5-F-C6H3)
1i, Ar = (3,5-CF3-C6H3)
1j, Ar = (3-Me, 4-F-C6H4)
1k, Ar = (4-NO2-C6H4)
1l, Ar = (4-Ph-C6H4)
11
12
1.1
0.6
(CH2Cl)2
MeCN
LiCl (1.0 equiv)
LiCl (1.0 equiv)
25
3c (8:2), 75
3d (9:1), 84
3e (9:1), 86
3f (9:1), 86
3g (9:1), 86
3h (9:1), 84
3i (9:1), 84
3j (8:2), 75
3a, 86e
13
14
15
16
0.6
MeCN
MeCN
MeCN
MeCN
LiCl (1.0 equiv)
LiCl (1.0 equiv)
LiCl (1.0 equiv)
LiCl (1.0 equiv)
NRf
0.6
NRg
(2b) 0.6
(2c) 0.6
3ab, 90
NR
a
Unless otherwise stated, all reactions were carried out at the 0.5
mmol scale with 1a (1.0 equiv) and 2a (1.1 equiv) stirring at ambient
temperature in MeCN irradiated for 6 h under open air. In entries 12-
16, 2a was used (0.6 equiv). Yields refer to the major isomer after
3k (9:1), 86
3l (9:1), 85
3m (8:2), 85b
3n (8:2), 73
b
1m, Ar = (4-PhO-C6H4)
1n, Ar = 2-(6-MeO-C10H6)
c
chromatographic purification. Reaction carried out under oxygen
d
balloon pressure. Reaction carried out in deaerated anhydrous
MeCN under an inert atmosphere. e CFL illumination also gave similar
yield. f Reaction carried out under a dark condition. g Reaction carried
out while heating at 45 C under a dark condition. NR = No reaction.
a
b
Yields refer to the major isomer after chromatographic purification. The
yield refers to Z:E mixture.
2 | J. Name., 2012, 00, 1-3
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With the optimized conditions in hand, the scope of the allenes 1e-n underwent phenylseleno-oxygenation effectively
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reaction with respect to aromatic allenes was investigated. The irrespective of the inductive effect ofDOthI:e10.m10e3t9a/C6aOnBd02p0a3r3aJ
corresponding results are summarized in Table 2.
substitution pattern and gave the respective products 3e-n in
According to the results, the reaction is tolerant of aromatic good to high yield (Table 2).
residues with electron-donating and electron-withdrawing Under typical conditions, the irradiation of 1,3-diallenyl
substituents. The sterically hindered substrate 2,4,5- benzene 4a provided the
,

'-diphenylselenyl product 5a in
trimethylphenyl allene 1d gave
,-unsaturated aldehyde 3d high yield (Table 3). Likewise, the heteroaromatic allenes 4b-c
in 84% yield, analogous to the yield obtained with yielded the expected products 5b11 and 5c in yields of 84 and
unsubstituted 1a (Table 2). The substituted aryl terminal 86%, respectively (Table 3).
Table 3. Scope of the reaction with respect to various allenes[a]
Substrate
Product
Substrate
Product
H
SePh
O
•
O
•
O
O
CH(OMe)2
CHO
SePh
SePh
O
H
4j
5j (80% single isomer)
•
4a
H
5a (85% single isomer)
SePh
O
O
•
SePh
O
N
N
O
H
•
CHO
CHO
H
4k
5j (80% single isomer)
4b
5b (84% single isomer)
H
O
H
O
•
•
O
N
O
CHO
N
N
SePh
SePh
4c
N
CHO
4l
5c (Z:E = 9:1, 86% major isomer yield)
5l (Z:E = 9:1, 84% major Z isomer)
O
O
H
Me
SePh
•
•
Me
O
•
O
H
SePh
4m
5d (83% single isomer)
5m (10:1, 80 % combined Z:E yield
4d
O
C6H5
O
SePh
H
O
O
H
O
•
C6H5
O
SePh
4n
5e (82% single isomer)
4e
5n (90%)
H
O
(p-MeO)C6H4
H
(p-OMe)C6H4
O
•
H
•
•
SePh
(Ph)2P
SePh
(Ph)2P
O
O
4o
5f (90% single isomer)
5o (~1:1, 92% isolated as Z:E mixture)
4f
Ph
H
(p-Cl)C6H4
H
Ph
O
(p-Cl)C6H4
O
•
(Ph)2P
SePh
(Ph)2P
SePh
O
O
4g
4p
5g (Z:E = 9:1) (90% major isomer)
5p (1:1 separable, 95% combined Z:E yield)
O
O
Ph
O
SePh
H
Ph
H
O
O
H
O
•
•
Ph
Ph
SePh
5q (90% isolated as 20:1, Z:E mixture)
4q
5h (82% single isomer)
4h
H
O
•
(HO)2B
4i
PhSe
SePh
5i (84% single isomer)b
a Yields refer to the major isomer after chromatographic purification. b The yield refers to 1.0 equiv of 4i and 1.1 equiv of 2a under otherwise
identical conditions as above.
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,-unsaturated allenes 4d-g were subjected to isomer. Further irradiation of 7b failed to give aldehyde.
Further,
photo-induced
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phenylselenyl-oxygenation
under
the Interestingly, under these reaction condDitOioI:n1s0,.1t0h3e9/bCr6oOmB0o20a3n3dJ
analogous conditions described above. It is noteworthy that in phenylselenyl groups in 6c were stable, but the isolated
all cases the products 5d-g were obtained as single regio- and product was an alcohol 7c in 84% yield, with no trace of the
stereoisomers in excellent yields with an exception of 5g that expected aldehyde (Table 4).
was formed as Z:E mixture (9:1) (Table 3). These results imply
that only terminal allenes could be functionalized under Table 5. Irradiation of benzyl allenes with 2aa
visible-light activation despite the presence of ,-unsaturated
Substrate
Product
Yield
SePh
double bond. Benzoate of buta-2,3-dien-1-ol 4h showed good
reactivity and led to product 5h as a single isomer in 82% yield.
Interestingly, allenylboronic acid 4i as a substrate furnished
•
9a (40% isolated as 3:1
Z:E mixture )b
SePh
8a
9a
the
3). Acetal 4j was submitted to irradiation. The product
identified was acetal-deprotected -unsaturated aldehyde 5j
,-diselenyl unsaturated aldehyde 5i in 84% yield (Table
9a (90% isolated as
3:1 Z:E mixture )
SePh
SePh
•
,
9b (95% single isomer)
in a yield of 80%. Next, allene 4k with an ortho-formyl
functional group was submitted to the reaction, and the
expected product 5j was isolated in 80% yield (Table 3).
Similarly, ortho-formyl allyloxy allene 4l gave desired product
5l in a yield of 84% (Table 3). We also evaluated the effect of
geminal substituted substrates 4m-p on the visible-light
induced phenylseleno-oxygenation process. As expected,
regardless of their substitution patterns, all of the substrates
resulted in an excellent yield of the products 5m-p as a Z:E
(1:1) mixture with the exception of 5m, which was obtained as
Z:E (10:1) mixture in a yield of 80% (Table 3). We also tested
1,3-diphenyl-1,2-propadiene 4q under the set standard
conditions and found the expected product 5q in 90% yield
with highly selectivity (Z:E = 20:1) (Table 3). This observation
indicates that the 1,3-substituted aryl allenes are also suitable
substrates for this transformation.
8b
8c
9b
9c
9c (93% isolated as 3:2
Z:E mixture)
SePh
SePh
•
a Reactions were carried out with 1.0 equiv of 8a-c and 1.1 equiv of 2a stirring
at ambient temperature in MeCN irradiated for 3 h under open air. b The yield
refers to 1.0 equiv of 8a and 0.6 equiv of 2a under otherwise identical
conditions as above.
To determine the necessity of the aryl group attached to the
allenic bond, we prepared 3-cycloalkyl-, 3-benzyl-, 3-benzyl-3’-
allyl attached terminal allenes 8a-c and irradiated them under
open air in a typical procedure.
Interestingly, in all cases the respective 3-cycloalkyl-, 3-benzyl-,
3-benzyl-3’-allyl 1-(phenylselenomethyl)vinyl selenides 9a-c
were isolated at good to high yields (Table 5). In other words,
these results signify that the allenic bond conjugation with the
aryl group or electron-withdrawing group is required to
intercept the molecular oxygen in this transformation.
However, the unsubstituted phenoxy allene 10a and N-(prop-
1,2-dienyl)-N-tosylbenzeneamide 10b gave phenol 11a and
aniline sulfonamide 11b as the sole product in 75% yield each.
No trace of the desired phenylseleno-formyl product was
observed. These reults can be rationalized on the basis of
capto-dative stabilization,12 wherein the radical cation is
Table 4. Study of thephenylselenyl oxygenation of hetero-atom allenesa
Substrate
Product
%yield
OH
SePh
O
•
O
7a (90%, 8:2 Z isomer
and 7aa mixture)
6a
7a
OH
O
SePh
7aa
Tos
Br
N
OH
SePh
•
Tos
Br
N
Ph
7b (82% single
Ph
stabilized by an adjacent -acceptor.
6b
isomer)
7b
SePh
SePh
h
White LEDs
7c (84% single
2a (0.6 equiv)
•
•
N
N
isomer)
X
X
MeCN
rt, open air
-acceptor
10a, X = O
4h
OH
•
PhSe
10b, X = N-Tos
7c
6c
a Reactions were carried out with 1.0 equiv of 6a-c and 0.6 equiv of
2a stirring at ambient temperature in MeCN irradiated under open
air
X
H-abstraction
or
NHTs
OH
(highly stabilised
neutral radical)
11b
11a
On the other hand, allene 6a provided an 8:2 ratios of alcohol
7a and 7aa. The photo-reaction of N-homo allenylsulfonamide
6b resulted in primary alcohol 7b as the only detectable
Scheme 2. SET initiated deprotection
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As a result, the highly stabilized neutral radical will result The monochromatic light (λmax at 365 nm) promoted,
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DOI: 10.1039/C6OB02033J
which in turn abstracts H-atom then, leading to observed chalcogen-centered radical additions to allenes are well-
product (Scheme 2).
documented.4a Therefore, we have conducted a control
experiment with 1a, 2a and TEMPO (1 equiv) under standard
conditions. Only the regular product 3a was observed, and no
trace of the TEMPO terminated products was detected under
these conditions, suggesting the SET pathway (Scheme 3).
h
White LEDs
H
•
O
PhSeSePh (0.6 equiv)
TEMPO (1.0 equiv)
LiCl (1.0 eqiuv)
SePh
1a
MeCN
rt, 3h
3a
Z:E = 9:1
Me
Me
TEMPO =
75% yield
N
O
Me
Me
Scheme 3. Radical trap experiment with 1a and 2a.
h
White LEDs (max = 430-730 nm)
PhSe-SePh
O
2a
*
R
SePh
[PhSe-SePh]
R = Phenyl, 3a
or
•
A
R
O2
substituted phenyl
O
O
SET
R
PhSe
+
OR
OH
R
SePh
SePh
•

+
E
F

PhSe-SePh
R
R
SePh
exciplex
B
R = 7a-c
LiCl
•


Li
+
PhSe-SePh
Cl
R
D
C
Scheme 4. Proposed mechanism for the phenylseleno-oxygenation
A plausible mechanism can be envisaged based on the In conclusion, we accomplished the chalcogenyl oxy-
aforementioned observations together with available prior functionalization of allenes attached to either aryl group or
data13 (Scheme 4). Upon visible-light irradiation 2a14 can attain electron withdrawing group with ambient air as a terminal
a singlet excited-state which can be reduced (-1.25 eV vs SCE in oxidant. This rection proceeds with high regio- and
MeCN)15 via a single electron transfer from ground state 1a stereoselectivity and produces the respective products in one-
(1.82 eV vs SCE in MeCN),16 resulting in exciplex
The exciplex in the presence of LiCl generates solvent water, hence considered eco-friendly reaction. Under the
separated ions A subsequent nucleophilic addition present reaction conditions, further oxidation of the aldehyde
and D 10
of phenylselenyl anion (PhSe_) to electron deficient radical group did not take place, indicating its mildness when
cation can lead to allyl-stabilized radical intermediate with compared to metal-based oxidation. To the best of our
simultaneous termination of phenylselenyl radical (PhSe-) to knowledge, the one-step syntheses of the
-heteroatom-
2a. The seleno-functionalized carbon radical may be functionalized -unsaturated aldehydes ketones and
susceptible to oxidation in the presence of molecular oxygen. diselenation adducts from the same starting material
As a result, the oxygen is trapped by carbon radical to form a promoted by visible-light photo-reaction are described here
peroxy-radical species , which then disproportionate to either for the first time. The synthetic utility of this strategy could
B formation. step in high yield. The by-product of this protocol is the benign
B
C
.
D
E

E
,
/
E
F
aldehyde (3a) or alcohol (7a-c), although it requires further well be conceived, and the results from this laboratory will be
experiments to elucidate the reaction pathways that lead to reported in due course.
their production.17
Conclusions
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Journal Name
(E)-3-Phenyl-2-(phenylselenyl)acrylaldehyde(3a):View ArticyleeOllnolinwe
Experimental Section
1
DOI: 10.1039/C6OB02033J
liquid; Rf = 0.40 (n-hexane:EtOAc = 98:2); 23 mg, (8% yield). H
NMR (500MHz, CDCl3): δ = 9.79 (s, 1H), 7.65-7.67 (m, 2H),
7.37-7.39 (m, 5H), 7.32 (s, 1H), 7.22-7.24 (m, 2H). 13C NMR
(100 MHz, CDCl3): δ = 189.0, 145.5, 138.4, 136.4, 134.7, 132.0,
129.8, 129.00, 128.6, 127.3, 126.6.
General Information: All reactions were conducted under open
air atmosphere. Apparatus used for reactions were oven dried.
THF was distilled over sodium benzophenone ketyl before use
and CH2Cl2 distilled over calcium hydride. MeCN purchased
directly from the commercial suppliers and used without
further purification. All other chemicals used were
commercially available. Progress of the reactions was
monitored by TLC on pre-coated silica gel 60 F-254 plates.
Evaporation of solvents was performed at reduced pressure on
a rotary evaporator. Column chromatography was carried out
with silica gel grade 60-120 and 100-200 mesh. 1H NMR
spectra were recorded at 300, 400 & 500 MHz and 13C NMR
All reactions were carried out with 2a, (0.6 mmol), allene (1.0
mmol) employing above typical procedure and the yields
reported based on the disappearance of respective allene.
3-Phenyl-2-(phenyltellenyl)acrylaldehyde (3ab): Irradiated for
6 h; Obtained as an inseparable mixture (Z:E = 9:1 by 1H NMR);
yellow oil; Rf = 0.5 (n-hexane:EtOAc = 97:3); 304 mg (90%
yield). 1H NMR (500 MHz, CDCl3): δ = 9.29 (s, 1H), 8.14 (s, 1H),
7.59-7.61 (m, 4H), 7.33-7.38 (m, 3H), 7.17-7.20 (m, 1H), 7.07-
7.10 (m, 2H). 13C NMR (100 MHz, CDCl3): δ = 193.4, 157.0,
141.4, 138.2, 135.2, 130.4, 130.0, 129.4, 129.2, 128.5, 128.2,
127.9, 124.3, 112.7, 29.7. IR (neat): 3056, 2920, 2849, 1682,
1564, 1435, 1106, 997, 734, 691 cm-1. HRMS (EI) calcd for
C15H12OTe [M+] 337.9950, found 337.9950.
75, 100 &125 MHz in CDCl3. Chemical shifts (

) are reported in
1
ppm. Tetramethylsilane (δ = 0.00 ppm for H) and CDCl3 (δ =
77.00 ppm for 13C) were used as the internal standard. Scalar
coupling constants (J) are reported in hertz (Hz). Mass spectral
data were compiled using MS (ESI), and High resolution mass
spectra (HRMS) were recorded by ESI probe in positive mode
using ORBITRAP analyzer. Electrochemical measurements were
performed on a PC-controlled CH instruments model CHI 620C
electrochemical analyzer. The experiments were performed in
a 1 mM phenyl allene solution in CAN at scan rate of 100 mV s-
1using 0.1 M tetrabutyl ammonium perchlorate (TBAP) as
supporting electrolyte. The working electrode was glassy
carbon, a standard calomel electrode (SCE) was the reference
electrode and platinum wire was an auxiliary electrode. After a
cyclic voltammogram (CV) had been recorded, ferrocene was
added, and a second voltammogram was measured. The UV
spectrum was recorded on a HITACHI U-2910 double beam
UV/VIS spectrophotometer. The 7W 6500K, 42mA (220-240Vac
50Hz) PHILIPS (Made in India) LED bulbs were used for
irradiation.
(Z)-2-(Phenylselenyl)-3-(p-tolyl)acrylaldehyde (3b): Irradiated
for 6 h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc = 95:5); 258
1
mg, (86% yield , Z isomer). H NMR (500 MHz, CDCl3): δ = 9.48
(s, 1H), 7.98 (s, 1H), 7.80 (d, J = 8.1 Hz, 2H), 7.37-7.39 (m,
2H),7.24 (d, J = 8.1 Hz, 2H), 7.18-7.20 (m, 3H), 2.39(s, 3H).13C
NMR (100 MHz, CDCl3): δ = 191.4, 153.3, 141.8, 131.6,
131.4,131.3, 130.9, 129.5, 129.2, 129.1, 127.1, 21.6. IR (neat):
1688, 1583, 1507, 1476, 1438, 1286, 1218, 1184, 1104, 1068,
1021, 810, 772, 737, 689 cm-1. HRMS (ESI) calcd for C16H15OSe
[M+H] 303.0283, found 303.0275.
(Z)-3-(4-(tert-Butyl)phenyl)-2-(phenylselenyl)acrylaldehyde
(3c): Irradiated for 6 h; yellow liquid; Rf = 0.25(n-hexane:EtOAc
= 95:5); 258 mg, (75% yield, Z isomer). 1H NMR (500MHz,
CDCl3): δ = 9.48 (s, 1H), 7.99 (s, 1H), 7.84 (d, J = 8.4 Hz, 2H),
7.45 (d, J = 8.5Hz, 2H), 7.37-7.39 (m, 2H), 7.18-7.20 (m, 3H),
1.33 (s, 9H).13C NMR (100 MHz, CDCl3): δ = 191.4, 154.8, 153.0,
131.6, 131.4, 131.2, 131.0, 129.5, 129.2, 127.1, 125.5, 35.0,
31.0. IR (neat): 1690, 1583, 1503, 1475, 1438, 1413, 1364,
1269, 1219, 1105, 1020, 829, 772, 737, 690 cm-1. HRMS (ESI)
calcd for C19H21OSe [M+H] 345.0752, found 345.0755.
Typical procedure for the synthesis (Z)-3-Phenyl-2-
(phenylselenyl)acrylaldehyde (3a): Diphenyldiselenide 2a
,
(187.3 mg, 0.6 mmol), 3-phenyl propa-1, 2-diene 1a (116.2 mg,
1.0 mmol) and LiCl (41mg, 1.0 mmol) were charged into a test
tube. While stirring, acetonitrile (4 mL, 0.01 M) was added and
the resulting homogeneous reaction mixture containing test
tube was placed into a beaker and irradiated with two 7W
white LED lamps under open air. After completion of reaction
(6 h), the reaction mixture was evaporated under vacuum to
give a residue which was purified over silica gel column
chromatography using n-hexane:EtOAc (95:5) as eluant to
afford the phenylseleno-oxygenation product 3a (247 mg,
86%) as yellow liquid along with minor isomer (23 mg, 8%).
Rf = 0.20;1H NMR (500 MHz, CDCl3): δ = 9.50 (s, 1H), 8.00 (s,
1H), 7.84-7.86 (m, 2H), 7.42-7.44 (m, 3H), 7.38-7.40 (m, 2H),
7.19-7.20 (m, 3H).13C NMR (125 MHz, CDCl3): δ = 191.4, 152.3,
134.2, 132.3, 131.9, 131.0 130.8, 129.2, 128.5, 127.3. IR (neat):
1684, 1586, 1565, 1475, 1441, 1391, 1287, 1211, 1180, 1110,
1068, 1022, 998, 924, 879, 736, 688 cm-1. HRMS (ESI) calcd for
C15H13O Se [M+H] 289.0126, found 289.0126.
(E)-3-(4-(tert-Butyl)phenyl)-2-(phenylselenyl)acrylaldehyde
(3c): yellow liquid; Rf = 0.35(n-hexane:EtOAc = 98:2); 40 mg,
1
(12% yield). H NMR (500MHz, CDCl3): δ = 9.82 (S, 1H), 7.82-
7.85 (m,2H), 7.63-7.67(m, 2H), 7.44-7.46 (m, 1H), 7.36-7.39 (m,
4H), 7.34(s,1H), 7.17-7.19(m,2H), 1.31(s,9H). 13C NMR (100
MHz, CDCl3): δ = 189.0, 158.7, 156.4, 153.0, 146.1, 143.9,
137.5, 136.1, 133.5, 132.0, 131.4, 131.2, 131.2, 130.3, 129.5,
129.2, 128.8, 127.1, 125.5, 125.3, 35.0, 31.1.
(Z)-2-(Phenylselenyl)-3-(2,4,5-trimethylphenyl)acrylaldehyde
(3d): Irradiated for 6 h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc
1
= 95:5); 277 mg, (84% yield , Z isomer). H NMR (500 MHz,
CDCl3): δ = 9.52 (s, 1H), 8.13 (s, 1H), 7.38 (s, 1H), 7.34-7.36 (m,
2H), 7.15-7.17 (m, 3H), 6.98 (s, 1H), 2.33 (s, 3H), 2.24 (s, 3H),
2.22 (s, 3H). 13C NMR (125 MHz, CDCl3): δ = 191.3, 151.1,
145.9, 139.4, 136.3, 135.1, 133.6, 132.3, 131.6, 130.7, 129.7,
129.0, 127.1, 19.7, 19.4, 19.3. IR (neat): 1692, 1578, 1496,
1475, 1442, 1385, 1271, 1193, 1113, 1022, 874, 739, 691cm-1.
6 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
HRMS (ESI) calcd for C18H18ONaSe [M+Na] 353.0415, found 7.01-7.06 (m, 1H), 2.29 (d, J = 2.0Hz, 3H); 13C NMR (100MHz,
View Article Online
DOI: 10.1039/C6OB02033J
CDCl3): δ = 191.3, 163.9, 161.3, 161.3, 151.6, 134.7, 131.7,
353.0410.
(Z)-3-(4-Methoxyphenyl)-2-(phenylselenyl)acrylaldehyde (3e): 131.5, 130.8, 130.7, 130.1, 130.0, 129.2, 129.1, 127.2, 125.3,
Irradiated for 6 h; yellow liquid; Rf = 0.25 (n-hexane:EtOAc = 125.1, 115.4, 115.1, 14.5. IR (neat): 1689, 1580, 1497, 1438,
95:5); 273 mg, (86% yield , Z isomer). 1H NMR (500 MHz, 1384, 1292, 1251, 1218, 1069, 1107, 1069, 999, 906, 819, 738,
CDCl3): δ = 9.48 (s, 1H), 7.95-7.97 (m, 3H), 7.36-7.38 (m, 2H), 690 cm-1. HRMS (ESI) calcd for C16H14OFSe [M+H] 321.0188,
7.18-7.20 (m, 3H), 6.94 (d, J = 9.0 Hz, 2H), 3.86 (s, 3H).13C NMR found 321.0183.
(100 MHz, CDCl3): δ = 191.6, 162.0, 153.6, 133.6, 131.2, 129.7, (E)-3-(4-Fluoro-3-methylphenyl)-2-
129.2, 128.8, 126.9, 126.8, 114.0, 55.4. IR (neat): 1685, 1601, (phenylselenyl)acrylaldehyde (3j): yellow liquid; Rf = 0.35 (n-
1
1582, 1562, 1507, 1475, 1438, 1297, 1257, 1177, 1123, 1103, hexane:EtOAc = 95:5); 32 mg, (10% yield). H NMR (500 MHz,
1026, 901, 829, 772, 738, 690 cm-1. HRMS (ESI) calcd for CDCl3): δ = 9.76 (s, 1H), 7.63-7.66 (m, 3H), 7.38-7.41 (m, 3H),
C16H15O2Se [M+H] 319.0232, found 319.0231.
7.24 (S, 1H), 7.00-7.01 (m, 2H), 2.26(S, 3H); 13C NMR (100MHz,
(Z)-3-(3, 5-Dimethoxyphenyl)-2-(phenylselenyl)acrylaldehyde CDCl3): δ = 188.7, 144.6, 138.0, 136.5,136.3,132.7, 130.6,
(3f): Irradiated for 6 h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc 129.8, 129.7, 129.0,128.8,126.6, 125.7, 115.2, 14.5.
1
= 95:5); 298 mg, (86% yield , Z isomer). H NMR (400 MHz, (Z)-3-(4-Nitrophenyl)-2-(phenylselenyl)acrylaldehyde
(3k):
CDCl3): δ = 9.47 (s, 1H), 7.92(s, 1H), 7.38-7.40 (m, 2H), 7.19- Irradiated for 6 h; yellow solid; Rf = 0.20 (n-hexane:EtOAc =
7.21 (m, 3H), 7.04(d, J = 2.2 Hz, 2H), 6.53-6.54 (m,1H), 3.79 (s, 95:5); 286 mg, (86% yield , Z isomer). 1H NMR (500 MHz,
6H). 13C NMR (125 MHz, CDCl3): δ = 191.3, 160.5, 152.2, 135.8, CDCl3): δ = 9.52 (s, 1H), 8.23 (d, J = 8.9 Hz, 2H), 7.99 (s, 1H),
132.4, 131.8, 131.4, 129.2, 127.2, 108.8, 103.4, 55.4. IR (neat): 7.87 (d, J = 8.5 Hz, 2H), 7.37-7.39 (m, 2H), 7.19-7.23 (m, 3H).13C
1685, 1573, 1455, 1424, 1345, 1301, 1258, 1202, 1152, 1105, NMR (125 MHz, CDCl3) δ = 190.6, 148.0, 146.3, 140.3, 136.9,
1059, 996, 837, 737, 686 cm-1. HRMS (ESI) calcd for C17H17O3 Se 132.7, 131.1, 129.5, 128.0, 127.8, 123.5. IR (neat): 1693, 1578,
[M+H] 349.0337, found 349.0332.
1517, 1476, 1438, 1344, 1289, 1100, 1069, 1020, 999, 887,
(Z)-3-(4-Fluorophenyl)-2-(phenylselenyl)acrylaldehyde (3g): 740, 690 cm-1. HRMS (EI) calcd for C15H11NO3Se [M+] 332.9904,
Irradiated for 6 h; yellow liquid; Rf = 0.25 (n-hexane:EtOAc = found 332.9914.
95:5); 263 mg, (86% yield , Z isomer). 1H NMR (500 MHz, (Z)-3-([1,
1'-Biphenyl]-4-yl)-2-(phenylselenyl)acrylaldehyde
CDCl3): δ = 9.49 (s, 1H), 7.95 (s, 1H), 7.87-7.90 (m, 2H), 7.36- (3l): Irradiated for 6 h; yellow solid. Rf = 0.25 (n-hexane:EtOAc
1
7.38 (m, 2H), 7.18-7.20 (m, 3H), 7.08-7.12 (m,2H).13C NMR = 90:10); 309 mg, (85% yield , Z isomer). H NMR (500 MHz,
(100 MHz, CDCl3): δ = 191.3, 165.2, 162.7, 151.1, 133.3,131.8, CDCl3): δ = 9.50 (s, 1H), 8.02 (s, 1H), 7.95 (d, J = 8.2 Hz, 2H),
130.4, 129.3, 129.0 127.3, 115.8,115.6. IR (neat): 1690, 1596, 7.61-7.66 (m, 4H), 7.44-7.47(m, 2H), 7.37-7.42 (m, 3H), 7.19-
1575, 1504, 1476, 1438, 1289, 1232, 1160, 1114, 1094, 1020, 7.21(m, 3H). 13C NMR (100 MHz, CDCl3): δ = 191.3, 152.0,
887, 831, 773, 738, 690 cm-1. HRMS (ESI) calcd for 143.5, 139.8, 133.0, 131.9, 131.8, 131.7, 129.3, 129.2, 128.9,
C15H11OFNaSe [M+Na] 328.9851, found 328.9853.
(Z)-3-(3,
128.0, 127.2, 127.0. IR (neat): 1689, 1579,1552,1482,1284,
5-Difluorophenyl)-2-(phenylselenyl)acrylaldehyde 1219, 1102, 1002, 900, 834, 771, 692 cm-1. HRMS (ESI) calcd
(3h): Irradiated for 6 h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc for C21H17OSe [M+H] 365.0439, found 365.0436.
1
= 95:5); 272 mg, (84% yield , Z isomer). H NMR (400 MHz, (Z)-3-(4-Phenoxyphenyl)-2-(phenylselenyl)acrylaldehyde
CDCl3): δ = 9.47 (s, 1H), 7.83 (s, 1H), 7.38-7.40 (m, 2H), 7.32- (3m): Irradiated for 6 h; obtained as an inseparable mixture
7.34 (m, 2H), 7.20-7.23 (m, 3H), 6.84 (m, 1H).13C NMR (125 (Z:E = 80:20); yellow liquid; Rf = 0.25 (n-hexane:EtOAc = 95:5);
1
MHz, CDCl3) δ = 190.8, 163.6, 163.5, 161.6, 161.5, 147.3, 137.1, 325 mg, (85% yield). H NMR (400 MHz, CDCl3): δ = 9.48-9.49
137.0, 136.8, 135.4, 132.6, 129.4, 128.1, 127.8, 113.4, 113.2, (d, J = 4.4 Hz, 1H), 7.95-7.97 (m, 1H), 7.89-7.93 (m 1H), 7.35-
105.8, 105.6, 105.4. IR (neat): 1692, 1615, 1578, 1473, 1435, 7.43 (m, 4H), 7.17-7.21 (m, 3H), 7.04-7.10 (m, 3H), 6.95-7.01
1319, 1226, 1120, 1045, 990, 851,738, 668 cm-1. HRMS (ESI) (m, 2H). 13C NMR (125 MHz, CDCl3) δ = 191.5, 186.5, 160.6,
calcd forC15H11OF2Se [M+H] 324.9938, found 324.9935.
160.3, 155.6, 155.4, 152.5, 144.7, 136.1, 133.4, 133.3, 131.5,
(Z)-3-(3, 5-Bis(trifluoromethyl)phenyl)-2- 131.3, 130.2, 130.1, 130.0, 129.8, 129.5, 129.2, 128.6, 127.1,
(phenylselenyl)acrylaldehyde (3i): Irradiated for 6 h; yellow 126.8, 124.7, 12.5, 120.2, 120.1, 119.7, 118.1, 117.8, 117.6. IR
liquid; Rf = 0.20 (n-hexane:EtOAc = 95:5); 355 mg, (84% yield , Z (neat): 1690, 1584, 1502, 1487, 1244, 1169, 1102, 1069, 872,
1
isomer). H NMR (400 MHz, CDCl3): δ = 9.55 (s, 1H), 8.11 (s, 745, 692, cm-1. HRMS (ESI) calcd for C21H16 O2NaSe [M+Na]
2H), 7.95 (s, 1H), 7.82 (s, 1H), 7.33-7.35 (m, 2H), 7.14-7.19 (m, 403.0208, found 403.0200.
3H).13C NMR (125 MHz, CDCl3): δ = 190.7, 145.7, 137.6, 136.1, (Z)-3-(6-Methoxynaphthalen-2-yl)-2-
132.9, 132.1, 131.9, 131.6, 131.3, 129.9, 129.5, 128.0, 127.5, (phenylselenyl)acrylaldehyde (3n): Irradiated for 6 h; yellow
124.0, 123.2, 121.8, 119.7. IR (neat): 1692, 1581, 1477, 1440, solid; Rf = 0.20 (n-hexane:EtOAc = 90:10); 268 mg, (73% yield).
1372, 1278, 1175, 1134, 940, 903, 739, 697 cm-1. HRMS (ESI) 1H NMR (400 MHz, CDCl3): δ = 9.54 (s, 1H), 8.27 (s, 1H), 8.12 (s,
calcd for C17H11OF6Se [M+H] 424.9874, found 424.9876.
(Z)-3-(4-Fluoro-3-methylphenyl)-2-
1H), 8.06-8.09 (m,1H), 7.78 (d, J = 8.9Hz, 1H), 7.73 (d, J = 8.7Hz,
1H), 7.40-7.43 (m, 2H), 7.17-7.20 (m, 4H), 7.12 (d, J = 2.5 Hz,
(phenylselenyl)acrylaldehyde (3j): Irradiated for 6 h; yellow 1H), 3.94 (s, 3H).13C NMR (100 MHz, CDCl3): δ = 191.5, 159.4,
liquid; Rf = 0.20 (n-hexane:EtOAc = 90:10); 240 mg, (75% yield , 153.5, 135.9, 132.7, 131.6, 130.7, 130.6, 129.6, 129.5, 129.2,
1
Z isomer). H NMR (400 MHz, CDCl3): δ = 9.48 (s, 1H), 7.92 (s, 128.1, 127.8, 127.1, 126.8, 119.6, 105.7, 55.4. IR (neat): 1684,
1H), 7.69-7.73 (m, 2H), 7.36-7.38 (m, 2H), 7.17-7.21 (m, 3H), 1624, 1565, 1478, 1438, 1416, 1390, 1345, 1269, 1224, 1175,
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Organic & Biomolecular Chemistry
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ARTICLE
Journal Name
1107, 1026, 998, 910, 854, 810, 737, 689 cm-1. HRMS (ESI) 7.68 (m, 2H), 7.60-7.63 (m, 1H), 7.51-7.54 (m, 2VHie)w, A7r.t4ic1le-O7n.l4in3e
13
DOI: 10.1039/C6OB02033J
calcd for C20H17O2Se [M+H] 369.0388, found 369.0380.
(m, 1H), 7.36-7.39 (m, 2H). C NMR (100 MHz, CDCl3): δ =
(E)-3-(6-Methoxynaphthalen-2-yl)-2-
189.8, 152.7, 137.3, 135.8, 133.4, 131.5, 129.7, 129.5, 128.9,
(phenylselenyl)acrylaldehyde (3n): yellow solid; Rf = 0.35 (n- 128.4, 126.6, 123.2; IR (neat) 1692, 1629, 1577, 1527, 1475,
hexane:EtOAc = 95:5); 44 mg, (12% yield). 1H NMR (500 MHz, 1440, 1376, 1330, 1295, 1215, 1157, 1084, 1059, 860, 742, 668
CDCl3): δ = 10.00 (s, 1H), 8.26 (s, 1H), 7.89-7.94 (m, 3H), 7.80- cm-1. HRMS (ESI) calcd for C16H13O2Se [M+H] 317.0075, found
7.82 (m, 2H), 7.23-7.26 (m, 2H), 7.16-7.19 (m, 2H), 3.97 (s, 3H). 317.0071.
13C NMR (100 MHz, CDCl3): δ = 192.0,160.2, 138.3, 134.2, (Z)-Benzyl
4-oxo-3-(phenylselenyl)but-2-enoate
(5e):
133.5, 132.3, 131.7, 131.1, 127.7, 125.1, 123.7, 120.0, 106.1, Irradiated for 6 h; colored liquid; Rf = 0.45 (n-hexane:EtOAc =
105.9, 55.5.
90:10); 283 mg, (82% yield , Z isomer). 1H NMR (500 MHz,
(2Z,
2Z')-3,
3'-(1,
3-Phenylene)-bis(2- CDCl3): δ = 9.18 (s, 1H), 7.62-7.64 (m, 2H), 7.34-7.41 (m, 7H),
(phenylselenyl)acrylaldehyde) (5a): Irradiated for 6 h; yellow 7.0 (s, 1H), 5.27 (s, 2H). 13C NMR (125 MHz, CDCl3): δ = 188.9,
solid; Rf = 0.15 (n-hexane:EtOAc = 85:15); 422 mg, (85% yield , 166.0, 150.9, 135.9, 135.3, 130.3, 129.7, 129.4, 128.6, 128.4,
1
Z isomer). H NMR (400 MHz, CDCl3): δ = 9.51 (s, 2H), 8.30 (s, 125.4, 122.0, 67.1. IR (neat): 1788, 1735, 1712, 1689, 1576,
1H), 8.0 (s, 2H), 7.82 (dd, J = 1.7,7.8 Hz, 2H), 7.5 (t, J = 7.8Hz, 1498, 1476, 1456, 1378, 1302, 1177, 1020, 966, 907, 850, 741,
1H), 7.36-7.38 (m, 4H), 7.18-7.21 (m, 6H).13C NMR (100 MHz, 694 cm-1. HRMS (ESI) calcd for C17H14O3NaSe [M+Na] 369.0000,
CDCl3) δ = 191.1, 150.2, 134.5, 133.6, 132.8, 132.6, 132.1, found 369.0007.
129.3, 128.8, 128.6, 127.5. IR (neat): 1689, 1576, 1475, 1437, (Z)-3-(Diphenylphosphoryl)-2-(phenylselenyl)acrylaldehyde
1388, 1281, 1175, 1108 1068, 1021, 998, 914, 772, 738, 689 (5f): Irradiated for 6 h; yellow solid; Rf = 0.50 (n-hexane:EtOAc
1
cm-1. HRMS (ESI) calcd for C24H18O2NaSe2 [M+Na] 520.9529, = 50:50); 370 mg, (90% yield , Z isomer). H NMR (400 MHz,
found 520.9535.
(Z)-2-(Phenylselenyl)-3-(pyridin-2-yl)prop-2-en-1-ol
CDCl3): δ = 10.9 (s, 1H), 7.56-7.58 (m, 2H), 7.50-7.54 (m, 4H),
(5bc): 7.38-7.48 (m, 9H), 6.49 (d, J = 18.3 Hz, 1H). 13C NMR (125 MHz,
Irradiated for 6 h and the solvent was evoporated under CDCl3): δ = 189.6, 189.5, 158.4, 137.2, 133.0, 132.2, 131.3,
reduced pressure. The resulting residue was dissolved in 130.8, 130.7, 130.6, 130.2, 129.9, 128.9, 128.7, 125.5. IR
methanol (20 mL) and cooled to 0 C. To this, cerium(III) (neat): 1967, 1894, 1676, 1548, 1478, 1436, 1370, 1278, 1193,
chloride heptahydrate (410 mg, 1.1 mmol) was added by 1118, 1049, 998, 774, 743, 694 cm-1. HRMS (ESI) calcd for
portionwise. To the resulting reaction mixture, sodium C21H18O2PSe [M+H] 413.0204, found 413.0206.
borohydride (42 mg, 1.1 mmol) was added and the combined (Z)-3-(Diphenylphosphoryl)-3-phenyl-2-
contents were stirred 0.5 h at 0 C. Then, saturated aqueous (phenylselenyl)acrylaldehyde (5g): Irradiated for 6 h; yellow
NH4Cl (20 mL) and allowed to ambient temperature. The solid; Rf = 0.50 (n-hexane:EtOAc = 50:50); 438 mg, (90% yield ,
aqueous layer was extracted with CH2Cl2 (2x20 mL). The Z isomer). 1H NMR (500 MHz, CDCl3): δ = 10.1 (s, 1H), 7.49-7.57
organic contents were dried over anhydrous Na2SO4, filtered (m, 9H), 7.37-7.41 (m, 5H), 7.27-7.32 (m, 2H), 7.21-7.25 (m,
and evoporated. The resulting residue was purified by silica gel 2H), 7.16 (t, J = 7.3 Hz, 2H), 6.77-6.79 (m, 2H). 13C NMR (125
flash column chromatography eluting with ethyl acetate/n- MHz, CDCl3): δ = 190.8, 152.9, 152.8, 136.3, 136.2, 132.3,
hexane (1:9) (Rf = 0.20) to give a brown oil 252 mg (86%yield). 132.2, 132.0,131.1, 130.3, 129.4, 129.0, 128.6, 128.4, 128.3,
1H NMR (400 MHz, CDCl3) δ = 8.71 (d, J = 4.4 Hz, 1H), 7.74-7.77 125.7. IR (neat): 1694, 1571, 1481, 1438, 1374, 1220, 1185,
(m, 2H), 7.65-7.69 (m, 1H), 7.37-7.42 (m, 1H), 7.30-7.35 (m, 1116, 1070, 1025, 999, 962, 922, 747, 696 cm-1. HRMS (ESI)
3H), 7.11-7.15 (m, 2H), 4.16 (d, J = 1.2 Hz, 2H), 1.82 (br.s, calcd for C27H22O2PSe [M+H] 489.0517, found 489.0514.
1H).13C NMR (100 MHz, CDCl3): δ = 155.4, 147.7, 141.9, 137.0, (Z)-3-Formyl-3-(phenylselenyl)allyl benzoate (5h): Irradiated
136.4, 129.1, 128.8, 128.2, 124.2, 122.8, 120.9. IR (neat): 3393, for 6 h; colored liquid; Rf = 0.20 (n-hexane:EtOAc = 90:10); 284
1
3053, 3009, 1609, 1585, 1553, 1470, 1428, 1369, 1306, 1217, mg, (82% yield , Z isomer). H NMR (400 MHz, CDCl3): δ = 9.42
1150, 1104, 1076, 999, 887, 843, 741, 694 cm-1. HRMS (ESI) (s, 1H), 8.00-8.07 (m, 2H), 7.58-7.62 (m, 1H), 7.45-7.52 (m, 4H),
calcd for C14H14ONSe [M+H] 292.0235, found 292.0228.
(Z)-2-(Phenylselenyl)-3-(pyrimidin-5-yl)acrylaldehyde
7.33 (t, J = 5.4 Hz, 1H), 7.25-7.29 (m, 3H), 5.19 (d, J = 5.4 Hz,
(5c): 2H). 13C NMR (125 MHz, CDCl3): δ = 188.7, 166.1, 152.1, 136.5,
Irradiated for 6 h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc = 133.4, 132.9, 131.5, 129.7, 129.5, 128.5, 128.2, 63.9. IR (neat):
90:10); 249 mg, (86% yield , Z isomer). 1H NMR (500 MHz, 1721, 1602, 1579, 1451, 1315, 1270, 1111, 1069, 1025, 973,
CDCl3): δ = 9.54 (s, 1H), 9.16 (s, 1H), 9.07 (s, 2H), 7.87 (s, 1H), 772, 712, 690 cm-1. HRMS (ESI) calcd for C17H14O3NaSe [M+Na]
7.38-7.40 (m, 2H), 7.20-7.25 (m, 3H). 13C NMR (125 MHz, 369.0000, found 368.9993.
CDCl3): δ = 190.2, 158.7, 157.3, 141.9, 137.6, 132.8, 130.2,
129.6, 128.7, 128.2, 127.6. IR (neat): 1693, 1573, 1548, 1476, In case of 5i, the reaction was carried out 2a (1.1mmol), allene
1411, 1315, 1217, 1190, 1103, 1068, 998, 919, 772, 744, 691 (1.0 mmol) employing above typical procedure and the yields
cm-1. HRMS (ESI) calcd for C13H11ON2Se [M+H] 291.0031, found reported based on the disappearance of respective allene.
291.0029.
(Z)-2, 3-Bis(phenylselenyl)acrylaldehyde (5i): Irradiated for 6
(Z)-4-Oxo-4-phenyl-2-(phenylselenyl)but-2-enal
(5d): h; yellow liquid; Rf = 0.20 (n-hexane:EtOAc = 95:5); 308 mg,
1
Irradiated for 6 h; pink liquid; Rf = 0.75(n-hexane:toluene = (84% yield , Z isomer). H NMR (500 MHz, CDCl3): δ = 9.28 (s,
5:95); 262 mg, (83% yield , Z isomer). 1H NMR (500 MHz, 1H), 8.83 (s, 1H), 7.61-7.63 (m, 2H), 7.49-7.51 (m, 2H), 7.37-
CDCl3): δ = 9.31 (s, 1H), 8.13 (s, 1H), 8.06-8.08 (m, 2H), 7.66- 7.41 (m, 3H), 7.25-7.27 (m, 3H). 13C NMR (100 MHz, CDCl3): δ =
8 | J. Name., 2012, 00, 1-3
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-1
186.3, 165.9, 133.6, 133.3, 133.1, 132.3, 131.9, 129.8, 129.3, 1504, 1252, 1176, 116, 1027, 773, 736, 697 cm ; HRMS (EI):
View Article Online
129.1, 127.5; IR (neat): 1675, 1576, 1535, 1476, 1438, 1377, calcd for C22H18O2Se [M+] 394.0472, founDdO3I9: 140..01043699/C. 6OB02033J
1233, 1157, 1101, 1021, 835, 770, 737, 690 cm-1. HRMS (ESI) (Z)-3-(4-Chlorophenyl)-3-phenyl-2-
calcd for C15H12ONaSe2 [M+Na] 390.9111, found 390.9107.
(phenylselenyl)acrylaldehyde (5p): Irradiated for
6
h;
(Z)-2-((3-Oxo-2-(phenylselenyl)prop-1-en-1-
Obtained as a separable mixture (Z:E = 50:50); yellow solid; Rf
1
yl)oxy)benzaldehyde (5j): Irradiated for 6 h; pale brown liquid; = 0.5 (n-hexane:EtOAc= 98:2); 189 mg, (47% yield). H NMR
Rf = 0.70 (n-hexane:EtOAc = 95:5); 265 mg, (80% yield , Z (500 MHz, CDCl3): δ = 9.42 (s, 1H), 7.35-7.37 (m, 2H), 7.25-7.32
1
isomer). H NMR (500 MHz, CDCl3): δ = 11.05 (s, 1H), 9.85 (s, (m, 4H), 7.12-7.18 (m, 8H). 13C NMR (125 MHz, CDCl3): δ =
1H), 7.78 (d, J = 2.1 Hz, 1H), 7.99 (s, 1H), 7.70 (dd, J = 2.2, 8.7 189.4, 163.9, 141.5, 137.8, 136.4, 135.5, 132.5, 132.3, 130.5,
Hz, 1H), 7.37-7.39 (m, 2H), 7.27-7.28 (m, 2H), 7.23-7.25 (m, 129.5, 128.7, 128.1, 127.0. IR (neat): 3056, 1900, 1672, 1438,
2H), 6.95 (d, J = 8.6 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ = 1117, 1089, 769, 736, 693 cm-1. HRMS (EI): calcd for
196.0, 161.5, 143.3, 139.8, 135.3, 131.8, 131.6, 129.4, 129.2, C21H15ClOSeM+] 397.9976, found 397.9966.
127.7, 127.2, 121.4, 119.8, 119.1. IR (neat): 1672, 1653, 1610, (E)-3-(4-Chlorophenyl)-3-phenyl-2-
1574, 1469, 1437, 1364, 1277, 1225, 1180, 1069, 1021, 897, (phenylselenyl)acrylaldehyde (5p): yellow solid; Rf = 0.6 (n-
1
833, 737, 691 cm-1. HRMS (EI) calcd for C16H11O3Se [M-H+]: hexane:EtOAc= 98:2); 189 mg, (48% yield). H NMR (500 MHz,
330.9873, found 330.9873.
(Z)-2-((4-oxo-3-(phenylselenyl)but-2-en-1-
CDCl3): δ = 9.41 (s, 1H), 7.30-7.47 (m, 1H), 7.36-7.40 (m, 2H),
7.26-7.28 (m, 3H), 7.10-7.22 (m, 8H).13C NMR (125 MHz,
yl)oxy)benzaldehyde (5l): Irradiated for 6 h; yellow liquid; Rf = CDCl3): δ = 127.04, 128.17, 128.46, 128.91, 130.24, 130.96,
0.45 (n-hexane:EtOAc = 80:20); 290 mg, (84% yield , Z isomer). 131.09, 132.50, 135.19, 135.72, 139.04, 140.14, 164.08,
1H NMR (500 MHz, CDCl3): δ = 10.49 (s, 1H), 9.46 (s, 1H), 7.86 189.70. IR (neat): 3056, 2922, 2851, 1666, 1483, 1440, 1117,
(dd, J = 1.8, 7.6Hz, 1H), 7.49-7.62 (m, 4H), 7.40 (t, J = 5.2 Hz, 1089, 767, 736, 693 cm-1. HRMS (EI) calcd for C21H15ClOSe [M+]
1H), 7.29-7.31 (m, 2H), 7.08 (t, J = 7.5Hz, 1H), 6.78 (d, J = 8.2 397.9976, found 397.9965.
Hz, 1H), 4.95 (d, J = 8.2 Hz, 2H).13C NMR (100 MHz, CDCl3): δ = 1,
3-Diphenyl-2-(phenylselenyl)prop-2-en-1-one
(5q):
189.4, 189.2, 159.9, 152.0, 136.9, 135.9, 135.3, 133.0, 129.6, Irradiated for 6 h; Obtained as an inseparable mixture (Z:E =
129.0, 128.1, 125.1, 121.6, 112.3, 67.5. IR (neat): 1689, 1600, 20:1); yellow oil; Rf = 0.5 (n-hexane:EtOAc = 98:2) 327 mg,
1
1578, 1479, 1459, 1395, 1287, 1240, 1160, 1067, 1020, 841, (90% yield). H NMR (500 MHz, CDCl3): δ = 7.08-7.17 (m, 3H),
740, 690cm-1. HRMS (ESI) calcd for C17H14O3NaSe [M+Na] 7.32-7.40 (m, 5H), 7.42-7.45 (m, 3H), 7.48-7.51 (m, 1H), 7.63-
369.0000, found 368.9999.
7.65 (m, 2H), 7.72-7.74 (m, 2H).13C NMR (125 MHz, CDCl3): δ =
Z:E mixture of 3-Phenyl-2-(phenylselenyl)but-2-enal (5m): 194.6, 138.8, 137.2, 136.9, 135.4, 134.6, 134.3,134.1, 133.4,
Irradiated for 6 h; Obtained as an inseparable mixture (Z:E = 132.5, 129.7, 129.5, 129.0, 128.5, 128.1, 127.9, 127.7. IR
10:1); yellow oil; Rf = 0.5 (n-hexane:EtOAc = 98:2) 242 mg, (neat): 3057, 2923, 2198, 1726, 1657, 1577, 1444, 1222, 738,
1
(80% yield ). H NMR (400 MHz, CDCl3): δ = 9.33 (s, 1H), 7.41- 688 cm-1. HRMS (EI) calcd for C21H16OSe [M+] 364.0366, found
7.44 (m, 5H), 7.18-7.30 (m, 5H), 2.60 (s, 3H). 13C NMR (125 364.0356.
MHz, CDCl3): δ = 189.5, 167.6, 139.7, 134.7, 133.6, 131.3, (Z)-4-Phenoxy-2-(phenylselenyl)but-2-en-1-ol (7a): Irradiated
129.3, 129.2, 128.5, 128.5, 126.8, 28.6. IR (neat): 3055, 1760, for 6 h; Obtained as a Z isomer 7a and internal double bond
1675, 1438, 1219, 1135, 770, 736, 691 cm-1. HRMS (EI) calcd attacked isomer 7aa in 8:2; yellow liquid; Rf = 0.75 (n-
1
for C16H14OSe [M+] 302.0209, found 302.0210.
hexane:EtOAc = 98:2); 287 mg, (90% yield , Z isomer). H NMR
3, 3-Diphenyl-2-(phenylselenyl)acrylaldehyde (5n): Irradiated (500 MHz, CDCl3): δ = 7.50- 7.57 (m, 2H), 7.24-7.32 (m, 6H),
for 6 h; Obtained as a yellow oil; Rf = 0.25 (n-hexane:EtOAc= 6.87-6.98 (m, 3H), 6.57-6.59 (m, 1H), 4.81 (d, J = 5.6 Hz, 2H),
98:2); 328 mg, (90% yield ). 1H NMR (400 MHz, CDCl3): δ = 9.43 4.15 (d, J = 1.1Hz, 2H). 13C NMR (100 MHz, CDCl3): δ = 158.2,
(s, 1H), 7.42-7.46 (m, 1H), 7.36-7.40 (m, 2H), 7.28-7.33 (m, 3H), 158.0, 138.8, 134.6, 134.0, 133.2, 131.5, 129.5, 128.1, 128.0,
7.24-7.27 (m, 2H), 7.18-7.21 (m, 4H), 7.12-7.14 (m, 3H). 13C 127.86, 123.7, 121.4, 121.1, 114.9, 114.7, 70.9, 67.1, 64.5,
NMR (125 MHz, CDCl3): δ = 190.0, 166.1, 141.9, 139.4, 134.7, 62.2, 48.5, 42.8. IR (neat): 3059, 1596, 1492, 1437, 1373, 1300,
132.2, 131.1, 130.9, 130.0, 129.6, 129.2, 128.9, 128.3, 127.9, 1212, 1171, 1073, 1014, 883, 734, 686 cm-1. HRMS (EI) calcd
126.8. IR (neat): 1729, 1674, 1441, 1294, 1117, 771, 698 cm-1. for C10H10O2Se [M-C6H6] 241.9846, found 241.9845.
HRMS (EI) calcd for C21H16OSe [M+] 364.0366, found 364.0356.
Z:E mixture of 3-(4-Methoxyphenyl)-3-phenyl-2- Phenylbenzenesulfonamide (7b): Irradiated for 6 h; yellow
(phenylselenyl)acrylaldehyde (5o): Irradiated for
(Z)-N-(4-Hydroxy-3-(phenylselenyl)but-2-en-1-yl)-4-methyl-N-
6
h; liquid; Rf = 0.25 (n-hexanes:EtOAc = 90:10); 387 mg, (82% yield,
1
Obtained as an inseparable mixture (Z:E = 50:50); yellow oil; Rf Z isomer). H NMR (500 MHz, CDCl3): δ = 7.48 (d, J = 8.2 Hz,
= 0.5 (n-hexane:EtOAc); 362 mg, (92% yield ). H NMR (500 2H), 7.27-7.31 (m, 6H), 7.18-7.25 (m, 4H), 6.99-7.01 (m, 2H),
1
MHz, CDCl3): δ = 9.43 (s, 1H), 9.36 (s, 1H), 7.11-7.46 (m, 24H), 5.88 (t, J = 7.2 Hz, 1H), 4.29 (d, J = 7.2 Hz, 2H), 4.01 (s, 2H), 2.44
6.88 (m, 2H), 6.78 (m, 2H), 3.84 (s, 3H), 3.81 (s, 3H). 13C NMR (s, 3H), 2.43(s, 1H). 13C NMR (100 MHz, CDCl3): δ = 143.7,
(125 MHz, CDCl3): δ = 190.0, 189.8, 166.6, 166.3, 161.5, 160.7, 138.8, 135.2, 134.0, 133.4, 133.0, 129.5, 129.4, 129.1, 128.8,
142.1, 139.8, 134.2, 133.4, 133.2, 133.1, 132.0, 131.8, 131, 3, 128.6, 128.2, 128.0, 127.7, 48.8, 42.5, 21.6. IR (neat): 3058,
130.1, 129.8, 129.3, 128.9, 128.3, 127.9, 126.7, 113.8, 113.3, 1595, 1491, 1438, 1348, 1258, 1162, 1090, 1067, 996, 928,
55.4, 55.3. IR (neat): 3054, 2925, 2839, 1713, 1669, 1600, 814, 770, 694, 658. HRMS (EI) calcd for C23H22 NO2SSe [M-OH]
456.0537, found 456.0552.
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Organic & Biomolecular Chemistry
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ARTICLE
(Z)-4-(5-Bromo-3-(phenylselenyl)-1H-indol-1-yl)-2-
Journal Name
Delhi) is gratefully acknowledged for awarding the fellowship
View Article Online
DOI: 10.1039/C6OB02033J
(phenylselanyl)but-2-en-1-ol (7c): Irradiated for 6 h; brown to S. V, K. A. and V. N. R. Also, thanks due to Dr. L. Giribabu (I &
liquid; Rf = 0.35 (n-hexane:EtOAc = 95:5); 485 mg, (84% yield , Z PC division) and Dr. P. R. Bangal (SEM division) for their help in
1
isomer). H NMR (500 MHz, CDCl3): δ = 7.76 (s, 1H), 7.54-7.56 recording electrochemical data, U.V. spectra and discussions.
(m, 2H), 7.28-7.37 (m, 5H),7.20-7.23 (m, 3H), 7.12-7.17 (m,
3H), 6.06 (t, J = 6.7 Hz, 1H), 4.89 (d, J = 6.7 Hz, 2H), 4.28 (s, 2H),
1.26 (br.s, 1H).13C NMR (125 MHz, CDCl3): δ = 135.4, 135.1,
134.8, 133.6, 133.4, 132.7, 132.0, 131.5, 129.6, 129.1, 128.7,
127.7, 125.8, 125.7, 123.3, 114.5, 111.2, 96.95, 45.02, 42.21.
HRMS (EI) calcd for C24H20BrNOSe2 [M+] 576.9059, found
576.9052.
Notes and references
1
(a) D. M. Schultz and T. P. Yoon, Science 2014, 343, 1239176; (b) J.
M. R. Narayanam and C. R. Stephenson, Chem. Soc. Rev. 2001, 40
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102; (c) M. Rechenthäler and A. G. Griesbeck, Adv. Synth. Catal.
2013, 355, 2727; (d) C. K. Prier, D. A. Rankic and D. W. C. MacMillan,
Chem. Rev. 2013, 113, 5322; (e) J. D. Nguyen, E. M. D. Amato, J. M.
R. Narayanam and C. R Stephenson, J. Nat. Chem. 2012, 4, 854; (f) D.
A. Di Rocco, K. Dykstra, S. Krska, P. Vachal, D. V. Conway and M.
Tudge, Angew. Chem., Int. Ed. 2014, 53, 4802.
D. Ravelli, S. Protti and M. Fagnoni, Chem. Rev. 2016, DOI:
10.1021/acs.chemrev.5b00662.
(a) H. Huo, X. Shen, C. Wang, L. Zhang, P. Röse, L.-A. Chen, K. Harms,
M. Marsch, G. Hilt and E. Meggers Nature 2014, 515, 100; (b) D. A.
DiRocco and T. Rovis, J. Am. Chem. Soc. 2012, 134, 8094; (c) M.
In case of 9a-c, the reactions were carried out 2a (1.1mmol),
allene (1.0 mmol) employing above typical procedure and the
yields reported based on the disappearance of respective
allene.
2
3
3, 4-Bis(phenylselenyl)but-2-enyl)benzene (9a): Irradiated for
3 h; Obtained as an inseparable mixture (Z:E = 3:1); yellow
liquid; Rf = 0.25 (n-hexane:EtOAc= 99:1); 400 mg, (90% yield).
1H NMR (400 MHz, CDCl3): δ = 7.41-7.57 (m, 4H), 7.15-7.26 (m,
10H), 6.99-7.04 (m, 2H), 6.06-6.10 (t, J = 7.6 Hz, 1H), 5.91-5.94
(t, J = 7.2 Hz, 1H), 3.86 (s, 2H), 3.73 (s, 2H), 3.57 (d, J = 7.2 Hz,
2H), 3.15 (d, J = 7.6 Hz, 2H); 13C NMR (125 MHz, CDCl3): δ =
134.7, 134.2, 133.3, 132.7, 131.5, 130.2, 129.7, 129.5, 129.4,
129.2, 129.0, 128.4, 127.7, 127.4, 127.1, 126.2, 126.1, 38.3,
37.8, 35.5, 31.2. IR (neat): 3057, 2997, 1575, 1474, 1435, 1020,
730, 686 cm-1. HRMS (EI) calcd forC22H20Se2 [M+] 443.9895,
found 443.9890.
(Z)-4-Cyclohexyl-2-(phenylselenyl)but-2-enylselanyl)benzene
(9b): Irradiated for 3 h; yellow oil; Rf = 0.25 (n-hexane:EtOAc =
98:2); 414 mg, (95% yield , Z isomer). 1H NMR (500 MHz,
CDCl3): δ = 7.44-7.46 (m, 4H), 7.20-7.25 (m, 6H), 5.55 (d, J = 9.1
Hz, 1H), 3.63 (s, 2H), 2.44-2.52 (m, 1H),1.58-1.63 (m, 2H), 1.49
(d, J = 15.7 Hz, 2H), 1.18-1.27 (m, 2H), 1.05-1.14 (m,1H), 0.91-
0.98 (m, 2H).13C NMR (100 MHz, CDCl3): δ = 144.1, 134.5,
132.6, 131.5, 129.1, 128.8, 127.7, 127.4, 126.5, 41.0, 37.9,
32.5, 25.8, 25.5. IR (neat): 3057, 2922, 2849, 1577, 1474, 1438,
1215, 1021, 753, 687 cm-1. HRMS (EI) calcd for C21H24Se2
[M+] 436.0208, found 436.0201.
Jouffroy, G. H. M. Davies and G. A. Molander, Org. Lett. 2016, 18
1606; (d) M. Jouffroy, C. B. Kelly and G. A. Molander, Org. Lett. 2016,
18, 876; (e) M. A. Cismesia and T. P. Yoon, Chem. Sci. 2015, , 5426.
,
6
4
(a) A. Ogawa, K. Yokoyama, H. Yokoyama, M. Sekiguchi, N. Kamble
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N. Sonoda and T. Hirao, J. Org. Chem. 1998, 63, 4277; (e) A. Ogawa,
R. Obayashi, N. Sonoda and T. Hirao, Tetrahedron Lett. 1998, 39
1577; (f) L. Yu, B. Chen and X. Huang, Tetrahedron Lett. 2007, 48
925.
,
,
5
(a) W. P. Todd, J. P. Dinnocenzo, S. Farid, J. L. Goodman and I. R.
Gould, J. Am. Chem. Soc. 1991, 113, 3601; (b) A. Z. Weller, Phys.
Chem. (Munich) 1982, 133, 93; (c) D. G. Whitten, C. Chesta, X. Ci, M.
A. Kellett and V. W. Yam, Adv. Photochem. 1986, 13, 237.
C. O. Laoire, S. Mukerjee, and K. M. Abraham, J. Phys. Chem. C. 2010,
114, 9178.
The 3-phenyl propa-1,2-diene, 1a exhibits its absorption maximum
at λmax = 285 nm in MeCN and the spectrum can be found in the
Supporting Information.
Diphenyl diselenide 2a has its absorption maximum (λmax) at 340 nm,
and the absorption reaches to 450 nm. Hence, the light absorbing
substrate is 2a only. a) U. Schmidt, A. Müller and K. Markau, Chem.
Ber. 1964, 97, 405; (b) O. Ito, J. Am. Chem. Soc.1983, 105, 850.
(a) S. Redon, A.-L. Berthe-Berkaoui, X. Pannecoucke and F.
Outurquin, Tetrahedron 2007, 63, 3707; (b) M. Yoshimatsu, K. Oguri,
K. Ikeda and S. Gotoh, J. Org. Chem. 1988, 63, 4475; (c) M.
Yoshimatsu and F. Hatanaka, Chem. Pharm. Bull. 2004, 52, 248.
6
7
8
9
2-(1,
2-Bis(phenylselenyl)ethylidene)pent-4-enyl)benzene
(9c): Irradiated for 3 h; Obtained as an inseparable mixture (Z:E
= 3:2); yellow oil; Rf = 0.25 (n-hexane:EtOAc = 99:1); 450 mg,
(93% yield). 1H NMR (500 MHz, CDCl3): δ = 7.09- 7.49 (m, 15H),
5.61-5.71 (m, 2H), 5.02-5.04 (m, 2H), 4.97-4.98 (m, 1H), 3.92 (s,
2H), 3.87 (s, 2H),3.82 (s, 2H), 3.33 (s, 2H), 3.10 (d, J = 6.4 Hz,
2H), 2.65 (d, J = 6.3 Hz, 2H).13C NMR (125 MHz, CDCl3): δ =
144.3, 143.9, 139.1, 138.7, 134.4, 132.8, 132.5, 129.2, 128.4,
127.5, 127.4, 127.1, 126.3, 126.2, 116.3, 42.3, 41.0, 37.2, 35.8,
33.7, 33.4. IR (neat): 3057, 2999, 2922, 2851, 1729, 1576,
1436, 1176, 1021, 772, 735, 690 cm-1. HRMS (EI) calcd for
C25H24Se2 [M+] 484.0208, found 484.0202.
10 (a) K. Mizuno, N. Ichinose, T. Tamai and Y. Otsuji, Tetrahedron Lett.
1985, 26, 5823; (b) K. Mizuno, N. Ichinose, T. Tamai and Y. Otsuji,
Chem. Lett. 1985, 455.
11 The isolated aldehyde 5c was unstable, hence reduced to alcohol
5bc under Luche conditions (CeCl3.7H2O/NaBH4 in MeOH, 0 C, 3 h)
and characterized as an alcohol.
12 (a) J. R. Lindsay-Smith and L. A. V. Mead, JCS Perkin.Trans. II, 1973
,
206; (b) J. R. Lindsay-Smith and D. J. Masheder, JCS Perkin Trans. II,
1976, 47; (c) H. G. Viehe, R. Mereny, Z. Stella and Z. Janousek,
Angew. Chem., Int. Ed. 1979, 18, 917.
13 (a) L. R. Byrd and M. C. Caserio, J. Am. Chem. Soc. 1971, 93, 5758; (b)
L. R. Byrd and M. C. Caserio, J. Org. Chem.1972, 37, 3881; (c) G.
Pandey and S. R. Gadre, Acc. Chem. Res. 2004, 37, 201; (d) G.
Pandey, M. K. Ghorai and S. Hazra, Pure. Appl. Chem. 1996, 68, 653;
Acknowledgements
We are grateful to Director, IICT, for constant encouragement.
Financial support was provided by the ORGIN (CSC-0108)
programme (CSIR) of XII five-year plan. UGC & CSIR (New
(e) G. Pandey, V. J. Rao and U. T. Bhalerao, Chem. Commun. 1989
,
39, 416; (f) G. Pandey, B. B. V. Soma Sekhar and U. T. Bhalerao, J.
Am. Chem. Soc. 1990, 112, 5650; (g) G. Pandey and B. B. V. Soma
Sekhar, J. Org. Chem.1992, 57, 4019; (h) G. Pandey and B. B. V. Soma
Sekhar, J. Org. Chem.1994, 59, 7367; (i) G. Pandey and K. S. S. P. Rao,
10 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
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Journal Name
ARTICLE
Angew. Chem., Int. Ed. 1995, 34, 2669-2671; (j) G. Pandey, K. S. S. P.
Rao, D. K. Palit and J. P. Mittal, J. Org. Chem.1998, 63, 3968.
14 PhSeSePh 2a did not show emission; hence we are unsuccessful to
collect the photo-physical data to support the electron-transfer (ET)
mechanism.
View Article Online
DOI: 10.1039/C6OB02033J
15 The E1/2 reduction potential for 2a, – 1.25 eV (Vs) SCE and E1/2
oxidation potential for 2a, 1.35 eV (Vs) SCE in MeCN was reported.
See ref. Electrochim. Acta.1983, 28, 1361.
16 The E1/2 reduction potential for 1a, – 1.22 eV (Vs) SCE and E1/2
oxidation potential 1a,  1.82 eV (Vs) SCE in MeCN was recorded.
Please see Supporting Information.
17 Presumably, peroxo-radical species
F benefits from phenyl
stabilization can lead long-lived peroxyl radical that undergoes 1,3-H
abstraction followed by decay to aldehyde. Whereas, lack of phenyl
stabilization might be resulting short-lived peroxyl radical with
concurrent self-termination results in alcohol. (a) K. G. Konya, T.
Paul, S. Lin, J. Lusztyk and K. U. Ingold, J. Am. Chem. Soc. 2000, 122,
7518; (b) S. Mitroka, S. Zimmeck, D. troya, and J. M. Tanko, J. Am.
Chem. Soc. 2010, 132, 2907.
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C6OB02033J
Visible-Light-Induced Phenylchalcogenyl-Oxygenation of Allenes Having Aryl- / or Electron
Withdrawing Substituent with Ambient Air as Sole Oxidant
Gullapalli Kumaraswamy*, Swargam Vijaykumar, Kukkadapu Ankamma and Vykunthapu Narayanarao
R2
R2
O
R2
XPh
hν
White LEDs
hν
White LEDs
•
PhXXPh (0.6 equiv)
XPh
PhXXPh (1.1 equiv)
XPh
H
LiCl (1.0 equiv)
MeCN, Open air
rt, 6-8h
R1
R1
(1.0 equiv)
LiCl (1.0 equiv)
rt, 3 h
deareated MeCN
Under innert
atmospher
R1
R2 = H, Ph, X= Se
R1 = H, R2 = H, X = Te
R1 = H, R2 = H, X = Se
45% yield
Z:E = 9:1, 70-92% yields
The stereoselective synthesis of α-phenylselenyl- or Telluryl β-aryl acryladehydes / ketones from aryl allenes /
1,3-diarylallene by an oxidative photo-induced single electron transfer process using benign ambient air as sole
oxidant was achieved.