3
(1m)
This work was financially supported by the Kansai
University Research Grants: Grant-in-Aid for Encouragement of
Scientists.
13
14
99 (2n)
Ph
Ph
O
Ph
Ph
References and notes
O
(1n)
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26 (2o)c
O
(1o)
CHO
15
96 (2p)
Ph
O
Ph
O
(1p)
a
Reaction conditions: oxirane (0.3 mmol), ReBr(CO)5 (5
mol%), CH2ClCH2Cl (2 mL), at 80 ºC for 1 h under an
atmosphere of N2.
b Isolated yield.
c 1H NMR yield.
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Based on these observations, the plausible reaction pathway
for the rhenium-catalyzed Meinwald rearrangement reaction of
oxiranes is shown in Scheme 2. First, the decarbonylation of
ReBr(CO)5 to form ReBr(CO)4, which is the coordinative
unsaturated 16-electron complex, is the first step of the catalytic
reaction.9 The coordination of rhenium species to the oxygen
atom of oxirane followed by the C-O bond cleavage of the
oxirane generates the stable carbocation.10 The hydrogen
migration from the carbocation smoothly proceeded to give the
corresponding carbonyl compound. On the other hand, when
phenyl is at the β-position of the carbocation, the phenyl group
will preferentially migrate through the well-established
phenonium ion to form the corresponding aldehyde.
ReBr(CO)5
- CO/∆
O
O
R3
R1
R2
ReBr(CO)4
R1
R2
R4
R4
R3
2
1
R3
R2
R3
R4
R1
O
ReBr(CO)4
R1
O
R4
R2
ReBr(CO)4
Scheme 2. A plausible reaction pathway
We showed that the rhenium complex catalyzed the Meinwald
rearrangement reaction of oxiranes to the corresponding carbonyl
compounds. The application of the reaction and determining the
reaction pathway are now in progress.
Acknowledgments