| Project/Area Number |
60850153
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| Research Category |
Grant-in-Aid for Developmental Scientific Research
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
TSUJI Jiro Tokyo Institute of Technology , Professor, 工学部, 教授 (00016685)
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| Co-Investigator(Kenkyū-buntansha) |
TAKAHASHI Takashi Tokyo Institute of Technology , Assistant, 工学部, 助手 (80110724)
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| Project Period (FY) |
1985 – 1986
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| Project Status |
Completed (Fiscal Year 1986)
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| Budget Amount *help |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1986: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 1985: ¥3,600,000 (Direct Cost: ¥3,600,000)
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| Keywords | Palladium-catalyzed reaction / <alpha> -Methylene ketone / <alpha> -Methylene lactone / Propargyl compound; Chiral cyclization; Vitamin <D_3> / 炭酸プロパルギル / 不斉環化反応 / 不斉還元反応 / プロスタグランジン【E_2】 / プロスタグランジン【D_2】 |
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| Research Abstract |
1. We developed general synthetic methods for <alpha> -methylene ketones and lactones, important functional group for biologically activity, by the palladium-catalyzed decarboxylation-deacetoxylation of allyl acetoxymethyl- <beta> -keto carboxylates. We also found several palladium-catalyzed reactions of propargyl compounds.
2. Optically active hydroindenone was synthesized as a precusor of vitamin <D_3> by palladium-catalyzed syn- <S_N> 2' cyclization of [Z,Z(22S,23R)]-ene oxide, prepared by Sharpless epoxidation. The formal butenylation was also carried out by palladium catalyzed allylation, followed by hydrogenolysis with formate.
3. Efficient chirality transfer was observed in the palladium-catalyzed cyclization of the methyl (3R)-methoxycarbonyloxy-(4E)-decenyl malonate and its (Z)-isomer to the (3R)-alkyl- <delta> -lactone and (3S)-lactone respectively.
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