| Budget Amount *help |
¥26,000,000 (Direct Cost: ¥20,000,000、Indirect Cost: ¥6,000,000)
Fiscal Year 2016: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2015: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2014: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2013: ¥11,830,000 (Direct Cost: ¥9,100,000、Indirect Cost: ¥2,730,000)
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| Outline of Final Research Achievements |
(1) Regioselective photochemical cycloadditions of silylene with azulene and guaiazulene gave bicyclic [4]dendralene and heptafulvene derivatives, respectively. A red-shifted absorption band of thus obtained [4]dendralene was observed, which is attributed to the orbital interactions between dendralene and a silacyclopropane moieties. (2) Thermal dearomative cycloaddition of silylene with pyridines to afford azasilepins was investigated. (3) We found a silanol-catalyzed formal C-H insertion of silylene with pyridine. This reaction proceeds via deprotonation of silanol by base-coordinated silylene. (4) Phosphenium cation and silylene are isolobal. Thus, we planned oxidation of phosphinyl radical to synthesize phosphenium cation for the dearomative cycloaddition. We obtained phosphaalkene-silver complex by the oxidation of phosphinyl radical with silver salts. We succeeded in the generation of dicoordinate antimony- and bismuth-centered radicals as persistent species.
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