| Project/Area Number |
20390002
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Chemical pharmacy
|
|---|
| Research Institution | Hokkaido University |
|---|
Principal Investigator |
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
NAKAMURA Seiichi 名古屋市立大学, 大学院・薬学研究科, 教授 (90261320)
ANADA Masahiro 北海道大学, 大学院・薬学研究院, 准教授 (90344473)
NAMBU Hisanori 北海道大学, 大学院・薬学研究院, 助教 (80399956)
|
|---|
| Project Period (FY) |
2008 – 2010
|
| Project Status |
Completed (Fiscal Year 2010)
|
| Budget Amount *help |
¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000)
Fiscal Year 2010: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2009: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2008: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000)
|
|---|
| Keywords | 合成化学 / 不斉触媒反応 / 固相遷移金属 / ロジウム(II)錯体 / ラジカル重合反応 / 1,3-双極付加環化反応 / ヘテロDiels-Alder反応 / カルベン / カルボニルイリド / ナイトレン / ルイス酸触媒 / 高分子担持型錯体 / C-H挿入反応 / Rawalジエン |
|---|
| Research Abstract |
(1) Rh_2(S-TCPTTL)_4 is an exceptionally effective catalyst for enantioselective tandem carbonyl ylide formation-cycloaddition reactions of 2-diazo-3,6-diketoesters with arylacetylene, alkoxyacetylene, and styrene dipolarophiles, providing cycloadducts in good to high yields and with enantioselectivities of up to 99% ee as well as with perfect exo diastereoselectivity for styrenes.
(2) A highly effective immobilization of Rh_2(S-PTTL)_4 has been achieved by copolymerization of dirhodium(II) complex-containing monomer with styrene and a flexible cross-linker. The immobilized catalyst promoted the intramolecular C-H insertion reaction at -78℃ with high enantioselectivity, and could be used for up to 100 sequential applications with a low leaching level (0.28 ppm).
(3) The hetero-Diels-Alder reaction between Rawal's diene and aldehydes under the influence of 1 mol % of Rh_2(S-BPTPI)_4 proceeded cleanly and gave, after treatment with acetyl chloride, the corresponding dihydropyranones in up to 99% ee.
|
