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COMMUNICATION
Journal Name
differently under different conditions. In the additive free pathway
for the synthesis of alkenes 2&3, intermediate A undergoes
DOI: 10.1039/C9CC00346K
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Scheme 4. a) Control experiments. b) Proposed mechanism.
a)
SMe
I
1
I2 (2.2 mmol)
80 oC, DMSO
I
2a, 83%
I
I
I2 (2.2 mmol)
DMSO
2
3
I
3a, 86%
O
I
Cl
I2 (2.2 mmol), 2N HCl
DMSO
A
4a, 77%
O
Cl
I2 (2.2 mmol), NaCl
DMSO
4
5
Cl
5a, 81%
O
SMe
I2 (2.2 mmol), TFA (1 mmol)
100 oC, DMSO
O
6a, 74%
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2018, 16, 3289-3302.
O
I2 (1 mmol), TFA (1 mmol)
100 oC, DMSO
6
SMe
1a
O
8, 71%
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b)
O
2HI+DMSO= I2+H2O+DMS
I
HCl
C
I2
rt
1
100 o
C
I
DMS
O
DMSO,
rt
O
,
I
2
I
Cl
SMe
I
3
I
4
I2, DMSO
I2
rt
SMe
I
A
O
O
I
SMe
Cl
2
6
O
Cl
I
I
2
5
rt
,
DMSO
MeI
S
I
O
NaCl
I
B
I2
I
DMS
80 o
I
C
I
D
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iodination to common iodonium intermediate B, that either at 80 oC
undergo conversion to 2 or at rt adds one more mole of iodine to 3.
However, in the presence of acid/NaCl, A intermediate reacts to
form mono- C and di-iodinated acetophenone D that ultimately led
of synthesis of 4 and 5 respectively. On the other hand, in the
presence of TFA, intermediate A through C can undergo S-
methylation followed by I2-DMSO mediated oxidation to compound
6.
In conclusion, we revealed different, efficient, atom economic,
economical, mild and novel synthetic method around
arylacetylenes for the generation of different isolable selective
products via I2-DMSO promoted unconventional reaction in a
different environment. Despite variation in the nature of
acetylenes, the reactions presented broad substrate scope. Further
study to expand its scope in one pot for generation of different
coupled products is currently underway in our lab
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Acknowledgment
S.A.R and A. K. thanks CSIR and University Grants Commission (UGC)
for the award of a JRF and SRF. This work was generously supported
by CSIR network project through grant no. HCP-0008. IIIM
communication no. IIIM/.
Zhang, Y. Wang,
S. Zhao, L. Lu, S. Yan and F. Yu,
DOI: 10.1021/acs.joc.8b02235.
Conflicts of interest
14. A. K. Padala, R. R. Kumar, S. Athimoolam and Q. N. Ahmed, Org. Lett.
2016, 18, 96−99.
There are no conflicts to declare.
Notes and references
4 | J. Name., 2012, 00, 1-3
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