Summary of Research Project Results under JSPS FY2001
"Research for the Future Program"

1.Research Institution Tohoku University
2.Research Area Physical and Engineering Sciences
3.Research Field Advanced Processes
4.Term of Project FY 1997 〜 FY 2001
5.Project Number 97P00302
6.Title of Project Convergent Molecular Transformation Process and Materials System

7.Project Leader
Name Institution,Department Title of Position
Yoshinori, Yamamoto Tohoku University, Graduate School of Science Professor

8.Core Members

Names Institution,Department Title of Position
Masahiko, Yamaguchi Tohoku University, Graduate School of Pharmaceutical Sciences Professor
Tokuji, Miyashita Tohoku University, Institute of Multidisciplinary Research for Advanced Materials Professor

9.Summary of Research Results

1. Development of convergent processes utilizing cross-benzannulation
Palladium catalyzed [4+2] cross-benzannulation of enynes with diynes was performed to give regiospecific cross-cycloaddition products in good to high yields. Phenol and aniline derivatives were also synthesized regiospecifically under the same methodology.
2. Development of convergent processes utilizing hydrocarbonation, hydroamination, and hydroalokoxylation
Palladium catalyzed hydrofurylation of alkylidenecyclopropanes was carried out to afford allylated furan derivatives effectively. Hydroamination and hydroalkoxylation were also developed. These methodologies can be used for preparation of useful compounds, such as aliphatic amines and alcohols, heterocycles, and cyclic ethers.
3. Development of convergent processes utilizing addition reactions to unsaturated compounds
Vinylation reactions of phenols, anilines, aromatic hydrocarbons, and enolates were developed using stoichiometric and, in some cases, catalytic amounts of tin or gallium reagents. Addition of phosphine or disulfide to alkynes or alkenes were conducted using palladium or rhodium catalysts.
4. Synthesis and properties of helical aromatic compounds
An optically pure helicene was prepared in multigram quantities, and various derivatives containing macrocyclic amides and alkynes were synthesized. Their properties regarding chiral recognition, asymmetric catalysis, chiral LB film formation, chiral CT complexation, and self-aggregation were examined.

10.Key Words

(1)Convergent Process、(2)Benzannulation、(3)Hydrocarbonation
(4)Pronucleophile、(5)Helicene、(6)LB film