| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
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| Outline of Final Research Achievements |
We attempted the following palladium(0)-catalyzed 'anti-Wacker'-type cyclizations of alkyne- or allene-containing electrophiles with organometallics: 1) asymmetric synthesis of cycloalkenols using chiral Lewis acid cocatalyst, 2) desymmetrization of diyne-aldehydes using chiral monophosphine ligand, and 3) chirality transfer of axially chiral allenic amines in situ generated by dynamic kinetic asymmetric allylic alkylation of primary amines with allenyl phosphates.
We also developed asymmetric alkylative cyclizations of alkyne-enals with organoboronic acids under the catalysis consisting of palladium, diarylprolinol, and catechol. Furthermore, we also demonstrated that pronucleophiles such as dimethyl malonate underwent not only 1,4-addition to conjugate enynes but also nucleophilic substitution with allenic alcohols under palladium catalysis in methanol solvent. The use of ketones as the pronuleophile in the latter reaction resulted in the direct formation of dihydrofurans.
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