Job/Unit: O43236
/KAP1
Date: 11-11-14 12:00:50
Pages: 6
S.-Y. Li, X.-B. Wang, N. Jiang, L.-Y. Kong
SHORT COMMUNICATION
Table 3. Scope of the heterodimerization reaction.[a]
Scheme 2. Proposed mechanism.
Conclusions
In conclusion, we developed a mild and practical proto-
col for the synthesis of 1,4-enediones from α-halo ketones
through a sodium sulfinate mediated reaction. This reaction
enables the construction of symmetric and unsymmetric
1,4-enediones with complete E selectivity. Further investiga-
tion into the reaction mechanism, scope, and application of
this strategy are currently underway in our laboratory.
Acknowledgments
This research was supported by the Project Funded by the Priority
Academic Program Development of Jiangsu Higher Education In-
stitutions (PAPD) and the Program for Changjiang Scholars and
Innovative Research Team in University (IRT1193).
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[a] The reactions were performed in two steps. First, a mixture of
3 (0.25 mmol), K2CO3 (0.75 mmol), 4-MeC6H4SO2Na (0.25 mmol),
and DMF (0.5 mL) was stirred at r.t. for 10 min; second, 4
(0.25 mmol) was added, and the mixture was stirred at r.t. for 12 h.
[b] Yield of isolated product.
and previous studies,[14] a possible pathway of the reaction
is illustrated in Scheme 2. Taking the elimination of 2-
bromoacetophenone (1a) as an example, initially, the reac-
tion of 1a with sodium 4-toluenesulfinate yields β-ketosul-
fone intermediate 6. Then, intermediate 6 is subsequently
deprotonated by K2CO3 to generate carbanion intermediate
7. Intermediate 7 reacts with 1a to afford intermediate 8.
Then, deprotonation of 8 generates 9, which subsequently
undergoes H-migration to yield 10. Reductive elimination
of 10 yields corresponding product 2a.
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