Development of tandem-type efficient organocatalysis based on the flexible catalyst structures: Application to the synthesis of natural products and drugs.

2015 Fiscal Year Final Research Report

• Project Area: Advanced Molecular Transformations by Organocatalysts
• Project/Area Number: 23105013
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo University of Agriculture and Technology
• Principal Investigator: Nagasawa Kazuo 東京農工大学, 工学(系)研究科(研究院), 教授 (10247223)
• Project Period (FY): 2011-04-01 – 2016-03-31
• Keywords: 有機触媒 / 酸化反応 / フリーデルクラフツ反応 / グアニジン / チオウレア / ウレア / 生理活性物質合成

Outline of Final Research Achievements

We have developed organocatalyst bearing guanidine and (thio)urea group, which are linked together through the chiral amino acids linkers. In this research, we have further examined the structure development of the catalysts and have applied the synthesis of natural products and anti-cancer drugs.
First, we have developed asymmetric oxidation of beta-ketoesters bearing tetralone skeleton in the presence of catalyst and CHP. In this reaction, high enantioselectivities were obtained. With the catalysis, daunorubicin and camptothecin were synthesized. This oxidation reaction was then applied to the kinetic resolution version. With the reaction, kinetic resolution took place, and corresponding beta-substituted products were obtained with high selectivity. This reaction was applied to the synthesis of (+)-linoxepin and (+)-rishirilide B. Finally, synthesis of dihydrolycoricidine was achieved based on entropy-dependent Friedel-Crafts reaction in the presence of organocatalyst.

Free Research Field

有機触媒、天然物合成