| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1999: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Research Abstract |
The single-electron releasable ate complexes (hereafter denoted as "SER-ate complex"), i.e., lithium trimethylmanganate (Me_3Mn(II)Li), lithium trimethylferrate (Me_3Fe(II)Li), and lithium trimethylcobaltate (Me_3Co(II)Li) have been designed and clarified. We also discussed the essence and mechanism of their single-electron transfer (hereafter called SET) reaction using ab initio theoretical calculations, in situ (ATR)FTIR spectroscopy, and electrochemical methods. The results clearly reveal that these complexes are powerful and selective complex reagents for the SET reaction and can control their single-electron releasing ability to some extent by the ligation environment. Based on the obtained electrochemical information, we also developed the catalytic version of this SET system. This system turned out to be effective for the desulfonylation of all types of N-phenylsulfonyl amides, the chemoselective deprotection of the O-allyl/benzyl/tosyl/t-butyldimethylsilyl (TBDMS) groups, the reduction of the nitro groups, the partial reduction of the carbonyl groups of diketone, the reductive ligand coupling of the diphenyliodonium salt, and the reductive diaryl coupling of the dihalogen compounds via anion radical species with good to excellent yields under mild conditions. This system is a very attractive method for several reasons (simplicity, good availability, low cost, and easy operation) and would be particularly useful for large-scale reactions.
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