| Project/Area Number |
05453129
|
|---|
| Research Category |
Grant-in-Aid for General Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Research Field |
有機工業化学
|
|---|
| Research Institution | Okayama University |
|---|
Principal Investigator |
SAITO Seiki Okayama University, Faculty of Engineering, Professor, 工学部, 教授 (60033239)
|
|---|
| Co-Investigator(Kenkyū-buntansha) |
ISHIKAWA Teruhiko Okayama University, Faculty of Engineering, Instructor, 工学部, 助手 (10263617)
井口 勉 岡山大学, 工学部, 助教授 (50168473)
|
|---|
| Project Period (FY) |
1993 – 1995
|
| Project Status |
Completed (Fiscal Year 1995)
|
| Budget Amount *help |
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1995: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 1994: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1993: ¥5,000,000 (Direct Cost: ¥5,000,000)
|
|---|
| Keywords | isocarbacyclin / Claisen-en sequence / phenyl vinyl sulfoxide / vinly ether formation / (4S)-4-OH-cyclopentenone / chiral homoallylic alcohol / acylsilane as COOH / アシルシラン / 分子内環化 / 光学活性4-TBSO-シクロペンテノン / 隣接ジオールコントローラー / 連続クライゼン-エン反応 / 鏡像体区別反応 / 速度分割 / 4塩化チタン / 不斉全合成 / Pd触媒ダブルカルボニル化 / アセチレン炭酸エステル / 置換シクロペンテノン |
|---|
| Research Abstract |
This research has established a novel, short-step, convergent, and practical method for the synthesis of isocarbacyclin featuring a one-pot, three-step process involving vinyl ether formation, Claisen rearrangement, and en reaction to give bicyclo [3.3.1]-backbone, which is not relying on any previous idea in this field that is principally the same as that for prostaglandin synthesis. The new method provided in this research can construct cyclopentenone framework bearing the homoallylic omega-chain longer by one-carbon at first followed by the introduction of the alpha-chain shorter by two-carbon to furnish the precursor for the bicyclo [3.3.1]-backbone. The method required (4S)-4-(O-tert-butyldimethylsilyl)-cyclopent-2-en-1-one as an important starting chiral compound, the antipode of which has been well-known starting material in PG synthesis. In other words, therefore, (4S)-isomer is given significant value which has not been experienced so far.
A chiral synthon corresponding to the homoallylic omega-chain has been synthesized efficiently from (S)-1,2-(O-isopropylidene) glycerol in twenty-gram scale and 80-95% yield for each step through a series of routine reactions (7 steps).
A precursor for the bicyclo [3.3.1]-backbone to be submitted to the one-pot, three-step process can be provided from an allylic tert-alcohol by vinyl ether formation. We hoped that a reaction to be used in this transformation should be free from mercury salts for some reasons and, after several attempts, has succeeded in developing a new, general method for the synthesis of vinyl ether from various allylic alcohols including tert-versions.
|
