| Project/Area Number |
06403025
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (A)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Synthetic chemistry
|
|---|
| Research Institution | Kyoto University |
|---|
Principal Investigator |
UTIMOTO Kiitiro Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90025958)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
TAKAI Kazuhiko Okayama University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (00144329)
OSHIMA Koichiro Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (00111922)
|
|---|
| Project Period (FY) |
1994 – 1996
|
| Project Status |
Completed (Fiscal Year 1996)
|
| Budget Amount *help |
¥36,200,000 (Direct Cost: ¥36,200,000)
Fiscal Year 1996: ¥5,600,000 (Direct Cost: ¥5,600,000)
Fiscal Year 1995: ¥5,600,000 (Direct Cost: ¥5,600,000)
Fiscal Year 1994: ¥25,000,000 (Direct Cost: ¥25,000,000)
|
|---|
| Keywords | DIMETALLIC REAGENT / STEREOSELECTIVE / CHIRAL ORGANOMETALS / ORGANOZINC COMPOUND / LEAD CATALYST / SILACYCLOBUTANE / ORGANOMANGANESE REAGENT / ORGANOSAMARIUM REAGENT / 低原子価金属塩 / 二ヨウ化サマリウム / マンガン / 四塩化チタン / アリルマグネシウム / ジヨードメタン / 有機亜鉛 / 立体選択的 / 希土類金属 / 高配位ケイ素 / タンタル / 有機希土類化合物 / 不斉合成反応 / 高選択的有機合成反応 / 金属触媒 |
|---|
| Research Abstract |
Investigators of this group extended the research on generation of new functionalized organometallic reagents and innovation on new synthetic methodologies using the reagents. Research was focused on the generation of multifunctional organometallic reagents, mainly dimetallic reagents, and the development of new highly selective reactions using multi-metal complex system. Main research results obtained within the term of the research project are follows.
1.Studies on gem-Dimetallic Reagents : Generation and Synthetic Applications.
A possibility of direct preparation of gem-dizinc reagents from gem-dihalides was suggested by the use of Pb-catalyzed reaction with Zn. Then, gem-dizinc reagents have been obtained in good yields. Dimetallic reagents thus obtained, RCH (ZnX)_2 where R=H,Me, Me_3Si etc, are useful in organic synthesis ; olefination of carbonyl compounds including ester, and stepwise reaction of electrophiles.
2.New Reactions using Organolanthanoid Reagents.
Generation of chiral a
… More
lpha-haloalkyl building block from achiral dihalides has been discovered : SmI_2-mediated reaction of 1,1-diiodoethane with chiral aldehydes gave chiral halohydrin in high diastereoselective manner. Chiral 1-iodoethyl reactive block was generated. Ethyl 2-bromoacetate gives ethyl 4-diiodosamario-3-oxo-butanoate selectively in low temperature, whose reaction with ketones and mixed anhydrides afforded hydroxy keto esters and diketo esters, respectively.
3.Organic Synthesis Using Functional Organosilicon Reagents.
Several synthetic reactions using silacyclobutane, dibromomethylsilanes, and acylsilanes have been disclosed. Various new carbon-carbon forming reactions have been studied, including threecomponent coupling of haloacylsilanes, acylsilane, and carbonyl compounds.
4.Use of Manganese in Organic Synthesis.
Some organic reactions using organomanganese and manganese ate-complexes have been studied ; organic synthesis using these manganese species in stereoselective addition to unsaturated bonds and reduction of organic halides were reported. Less
|
