Oxidative Generation of Isobenzofurans for Intermolecular Cycloadditions.
Emi Nakatsugawa1, Keigetsu Higashiyama1, Hiroyuki Yamakoshi1
1Graduate School of Pharmaceutical Sciences, Nagoya City University, 3-1, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan.
Phthalans undergo tandem oxidation and Diels-Alder reactions to form oxygen-bridged polycycles. This efficient synthesis uses 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and manganese(III) acetate for catalytic oxidation.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Phthalans are precursors to isobenzofurans.
- Isobenzofurans are reactive intermediates in Diels-Alder reactions.
Purpose of the Study:
- To investigate a tandem oxidation/Diels-Alder reaction of phthalans.
- To develop a catalytic method for synthesizing oxygen-bridged polycycles.
Main Methods:
- Oxidation of phthalans using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ).
- In situ generation of isobenzofurans.
- Diels-Alder reaction with dienophiles (e.g., benzoquinone).
- Catalytic oxidation using manganese(III) acetate (Mn(OAc)3).
Main Results:
- Successful synthesis of oxygen-bridged polycycles from phthalans.
- Modest to good yields achieved.
- Catalytic system using Mn(OAc)3 demonstrated.
- Portionwise addition of DDQ optimized for reactive phthalans.
Conclusions:
- A novel tandem reaction sequence for phthalans was established.
- The reaction provides efficient access to complex oxygen-bridged polycycles.
- Catalytic oxidation offers a more sustainable synthetic approach.
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