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Green Chemistry
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ARTICLE
Journal Name
DOI: 10.1039/C9GC03619A
Scheme 5. Salt free two step catalytic synthesis of spirocyclic
derivatives
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O
O
O
2 % [Ni]
A : 1 mol%
OH
3
4
5
+
Toluene
reflux, 18 h
MeOH
80 °C; 1 night
- H2O
94 %
86 %
- C2H4
7e
N
Ru
Cl
Cl
A :
Cy3P
6
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Conclusion
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8
9
In summary, the first efficient nickel catalyzed α-allylation of
ketones with allyl alcohol has been developed. The reaction is
performed under neutral conditions without addition of any
additive or base and water is the sole by-product. After
optimization of reaction conditions, various allylic ketones
have been synthesized. Acyclic as well as five and six
membered cyclic ketones have been efficiently converted
according to this salt free nickel catalysed protocol.
Diallylether proved to be an alternative suitable reagent and
beyond the synthetic interest, this reactivity shows that the
self-etherification of allyl alcohol is not competing with the -
allylation of ketones. Finally, the nickel catalyzed -allylation
of ketone with allyl alcohol is a key step that opens the way to
the synthesis of spirocyclic derivatives according to a two step
protocol that involves salt free catalytic transformations.
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6 | J. Name., 2012, 00, 1-3
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