3
a
Table 2. Examination of the reaction scope.
R
R
R
O
R'
O
ZnCl2 (10 mol %)
Sn
4 R'
4
R
1
,4-dioxane
Cl
1
2
3
R
b
Alkynyl ketones 3
R
R’
Ph
4-t-BuC
3-MeOC
T (°C)
80
Time (min)
Yield (%)
3
3
3
3
3
3
3
3
3
3
3
3
3
aa
ab
ag
bb
ac
ad
ae
af
Ph
150
75
100
60
30
10
20
30
20
30
10
10
30
67
Ph
6
H
4
80
80
Ph
6
H
4
80
66
4-MeC
Ph
6
H
4
4-t-BuC
Me
6
H
4
80
63
40
99
Ph
Pr
60
81
Ph
i-Pr
60
78
Ph
CH
Me
Me
Pr
3
(CH
2
)
14
60
95
bc
dc
bd
ce
cf
4-MeC
Bu
6
6
H
4
4
40
87
40
74
4-MeC
H
60
88
4-ClC
6
H
4
i-Pr
CH
60
85
4-ClC
6
H
4
3
(CH
2
)
14
60
89
a
b
Reagents and conditions: (RC≡C)
4
Sn 1a (0.55 mmol), R'C(O)Cl 2a (2.0 mmol), ZnCl
2
(0.2 mmol), 1,4-dioxane (0.72 mL). Isolated yield.
The reaction of stannanes 1 with other lipophillic acid
3452–3458.
7
8
9
1
R. Harigae, K. Moriyama and H. Togo, J. Org. Chem., 2014, 79,
049–2058.
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1615-1619.
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Green Chem., 2011, 13, 3238–3247.
chlorides required heating at 60 °C; the reaction was complete
within 10-30 minutes, furnishing acetylenic ketones 3a-x in good
yields (78-95%). It should be noted that long-chain lipophillic
acid chlorides also reacted well to give the corresponding long-
chain ketones in high yields (see Table 2 and ESI, Table 1).
2
0
In summary, we have proposed a new, fast and atom-
economical method for the preparation of α-acetylenic ketones,
starting from mild nucleophilic reagents – tetraalkynylstannanes.
The method is suitable for the synthesis of long-chain acetylenic
ketones.
11
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1
1
15
3
4
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The publication was financially supported by the Russian
Ministry of Education and Science (grants of the President of the
Russian Federation СП-2272.2016.1). This work was performed
with the use of equipment of the Research and Educational
Centrum “Diagnostics of the structure and properties of
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1
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7
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