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Green Chemistry
Page 4 of 5
DOI: 10.1039/C6GC03168D
COMMUNICATION
Journal Name
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9
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O
O
A
H
O
S
1.2 eq DMC
0.3 eq KOMe
H/D
O
+
D3C
CD3
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1a
3aa-d1
2.0 eq
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94 % deuterium incorporation
,
O
B
D
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O
S
1.2 eq DMC
0.3 eq KOMe
H/D
+
H3C
CH3
O
O
12 F. Sasse, B. Böhlendorf, M. Herrmann, B. Kunze, E. Forche, H.
Steinmetz, G. Höfle, H. Reichenbach and M. Hermann, J.
Antibiot. (Tokyo), 1999, 52, 721–729.
1a-d1
3aa-d1
2.0 eq
0 % deuterium incorporation
13 K. Gerth, H. Irschik, H. Reichenbach and W. Trowitzsch, J.
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14 B. A. Kundim, Y. Itou, Y. Sakagami, R. Fudou, T. Iizuka, S.
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16 RÖMPP Online,
O
C
D
5.0 eq DMC
0.3 eq KOMe
H/D
no
DMSO
+
O
O
3aa-d1
96 % deuterium incorporation
1a-d1
02102, (accessed April 2016).
17 M. Bassetti and B. Floris, J. Chem. Soc. Perkin Trans. 2, 1988,
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Scheme 3 Deuterium labeling experiments.
In contrast, the deuterium incorporation was 96% for the
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reaction of d1-phenylacetylene (1a-d1) in the absence of DMSO
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(Scheme 3 C), indicating that the alkyne proton is transferred
to the product in case no other proton source is available.
Conclusions
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The alkoxide-catalyzed addition of alkyl carbonates to terminal
alkynes represents an efficient approach for the
stereoselective synthesis of synthetically valuable (E)-
methoxyacrylates. The protocol offers a broad substrate scope
covering broad range of functionalized arenes and
β-
a
heteroarenes. Due to its remarkably high atom economy and
low E-factor, this synthetic route is highly sustainable and
interesting also for industrial applications.
26 P. Tundo and M. Selva, Acc. Chem. Res., 2002, 35, 706–716.
27 Environmental Protection Agency, 2009, (EPA-HQ-OAR-2006-
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30 EP, 0525516A2, 1993.
31 R. A. Sheldon, Green Chem., 2007, 9, 1273–1283.
Acknowledgments
,
We thank A. Konkel for technical assistance and the Fonds der
Chemischen Industrie (fellowship to T.W.) and the Deutsche
Bundesstiftung Umwelt (fellowship to E.R.) for financial
support.
Notes and references
1
2
3
4
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,
4 | J. Name., 2012, 00, 1-3
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