Highly selective synthetic organic reactions utilizing cleavage of C-Cl bond
| Project/Area Number |
20550036
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Organic chemistry
|
|---|
| Research Institution | Shinshu University |
|---|
Principal Investigator |
NISHII Yoshinori Shinshu University, 繊維学部, 准教授 (40332259)
|
|---|
| Project Period (FY) |
2008 – 2010
|
| Project Status |
Completed (Fiscal Year 2010)
|
| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2010: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2009: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2008: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
|
|---|
| Keywords | 有機反応化学 / ナフレンリグナン / ジヒドロナフタレン / 環拡大反応 / ベンズアヌレーション / シクロプロパン / 炭素-塩素結合切断 / procumphthalide A / Cyclogalgravin / 高立体選択的 / 高位置選択的 / 不斉変換 / 軸不斉 / 炭素塩素結合 / クロロシクロプロパン / ジクロロシクロプロパン / α-クロロエステル / Reformatsky反応 / アシル化 |
|---|
| Research Abstract |
1) We developed a stereoselective synthesis of cyclopropane derivatives utilizing a highly stereoselective SMI_2-promoted Reformatsky-type reaction and acylation of 1-chlorocyclopropanecarboxylic esters. The present method is a new avenue for the stereoselective synthesis of highly substituted cyclopropylcarbonyl compounds. Utilizing radical formylation and the present protocols, we achieved a highly stereoselective double-carbon elongation on the dichloro- carbon of gem-dichlorocyclopropanes. We also developed a stereoselective synthesis of cyclopropane derivatives utilizing a highly stereoselective SmI_2-promoted C-silylation and alkylation of 1-chlorocyclopropane- carboxylic esters. Based on the fact that no O-TMS-product was obatained, a SmI_2-O-enolate might not be generated or should exist as a particular intermediate that can not react with TMSCl on oxygen atom. 2) We developed a novel synthesis of 1-aryl-1,2-dihydronaphthalene-3-carboxylic acid esters utilizing a Lewis acid-mediated regioselective ring-expansion of methyl (aryl-hydroxymethyl)cyclopropanecarboxylate. Application of the present method to a total synthesis of natural product is now being performed. 3) We achieved the first total synthesis of a novel (±)-6'-methoxyretrojusticidin B, which was proposed as procumphthalide A, utilizing regiocontrolled benzannulation of an aryl(aryl')-2,2-dichlorocyclopropylmethanol as the key step. 1H-NMR spectral data suggested that the structure of the synthesized product, 6'-methoxyretrojusticidin B, was inconsistent with that of natural procumphthalide A. The revised structural elucidation of natural procumphthalide A was concluded to be 5'-methoxyretrochinensin.
|
Report
(4 results)
Research Products
(31 results)
-
-
[Journal Article] Lewis Acid-mediated Highly Regioselective Ring-expansion of Methl 2-Phenyl-1-(arylhydroxymethyl)cyclopropa necarboxylates2010
Author(s)
Yoshida, E., Nishida, K., Toriyabe, K., Taguchi, R., Motoyoshiya, J., Nishii, Y.
-
Journal Title
Chem.Lett. 39
Pages: 194-195
Related Report
Peer Reviewed
-
-
-
-
-
-
-
[Journal Article] Practical, general, and systematic method for optical resolution of gem-dihalo- and monohalocyclopropanecarboxylic acids utilizing chiral 1,1'-binaphtholmonomethyl ethers : Application to the synthesis of three chiral pesticides2008
Author(s)
Hiroaki Yasukochi, Takayuki Atago, Akihiro Tanaka, Hidefumi Nakatsuji, Eri Yoshida, Akikazu Kakehi, Yoshinori Nishii, Yoo Tanabe
-
Journal Title
Org.Biomol.Chem. 6
Pages: 540-547
Related Report
Peer Reviewed
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
