Studies on Highly Stereoselective Synthetic Process Based on Palladium-Catalyzed Reactions for Biologically Active Compounds

基于钯催化反应的高立体选择性生物活性化合物合成工艺研究

• 批准号: 60850153
• 负责人: TSUJI Jiro
• 金额: $ 4.61万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research
• 财政年份: 1985
• 资助国家: 日本
• 起止时间: 1985 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-60850153/
• 关键词: 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】

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.

1.我们发展了<alpha>钯催化的烯丙基乙酰氧基甲基- -酮羧酸酯脱羧-脱乙酰氧基反应合成重要生物活性官能团--亚甲基酮和内酯的一般方法<beta>。我们还发现了几个钯催化的炔丙基化合物的反应.通过<D_3>夏普<S_N>利斯环氧化制备的[Z，Z（22 S，23 R）]-氧化烯在钯催化下进行顺-2 '环化反应，合成了具有光学活性的维生素前体氢茚酮。还通过钯催化的烯丙基化反应，然后与甲酸酯氢解进行了丁烯的正式化.在钯催化的环化反应中，（3R）-甲氧羰氧基-（4 E）-丙二酸癸烯酯及其（Z）-异构体分别生成（3R）-烷基-<delta>β-内酯和（3S）-内酯。

项目成果

TSUJI Jiro: Tetrahedron Letters. 27. 2483-2486 (1986)

辻二郎：四面体字母。

Jiro TSUJI: "Palladium-Catalyzed Preparation of 1,2-Dienes by Selective Hydrogenolysis of Alk-2-ynyl Carbonates with Ammonium Formate." the Journal of The Chemical Society, Chemical Communications. 118-119 (1986)

Jiro Tsuji：“通过甲酸铵选择性氢解烷基碳酸酯制备 1,2-二烯”。

Jiro TSUJI: "New General Synthetic Methods Involving <pi> -Allylpalladium Complexes as Intermediates and Neutral Reaction Conditions." Tetrahedron. 42. 4361-4401 (1986)

Jiro TSUJI：“涉及 <pi> -烯丙基钯配合物作为中间体和中性反应条件的新通用合成方法。”

TSUJI Jiro: Synthesis. 623-627 (1986)

辻二郎：综合。

Jiro TSUJI: "Facile Palladium-Catalyzed Decarboxylation Reaction of Allylic <beta> -Keto Esters." The Journal of Organic Chemistry. 50. 3416-3417 (1985)

Jiro TSUJI：“烯丙基 <β>-酮酯的轻松钯催化脱羧反应。”