Studies on the Synthesis of Physiological Active Terpenes and Development of New Synthetic Methods

生理活性萜烯的合成研究及新合成方法的开发

• 批准号: 62570954
• 负责人: YAMAKAWA Koji
• 金额: $ 1.73万
• 依托单位: Tokyo University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-62570954/
• 关键词: Terpenes; Microbial Oxidation; alpha-Methylene-gamma-lactones; Synthesis of Marine Natural Products; Cembranes; alpha, beta-Epoxy Sulfoxides; Asymmetric Synthesis; N-Arylaziridines; テルペン類; α-メチレン-γ-ラクトン; センブラン類; α,β-エポキシスルホキシド; N-アリ-ルアチリジン; セ

1.Synthesis of the Physiological Active Terpenes. (1)Synthesis of Eudesman-alpha-methylene-6,12-olide and -8,12-olide by Intra molecular Cycization of Allylic Silylated Aldehydes. (2)Synthetic Method of alpha-Methylene-gamma-lactones Fused to Medium and Large Membered Rings by Intramolecular Cyclization of Formylated Allylhalide (3)Synthesis of Physiological Active Eremophilanes: Cinalyratol Acetate, Aristol-9-en-3-ol and Debneyol.2.Studies on the Microbial Transformations of alpha-Santonin and 11-Dehydro- alpha-santonin. (1)Microbial Hydroxylation of Santonin by Asoeriaus niger. (2)Microbial Hydroxylation of 11- Dehydrosantonin by Asperigus niger.3. alpha,beta-Epoxy Sulfoxides as Useful Intermediates in Organic Synthesis. (1)A Novel Synthesis of alpha-Substituted Carbonyl Compounds, alpha,beta-Unsaturated Ketones, and Esters from Carbonyl Compounds with Carbon Homologation Through alpha,beta-Epoxy Sulfoxides. (2)Magnesium Salt Induced Opening of alpha,beta-Epoxy Sulfoxides. Synthesis of alpha-Chloroketones, alpha-Alkoxyketones. (3)A Novel Synthegis of alpha-Acyl-, 3-Keto-, and Spiro-Cyclic Ethers via Ring-opening alpha,beta-Epoxy Sulfoxides by Hydroxyl Group. (4)A Novel Steroselective Synthesis of (E 1-Acylbutadienes from 1-Chloro alkyl Phenyl Sulfoxides and 4-(Phenylthio)butanal Through alpha,beta-Epoxy Sulfoxides . (5)A Novel Method Annulation Through alpha,beta- Epoxy Sulfoxides with aid of Intramolecular Radical Cyclization. (6)A Novel Synthesis of Aldols and Through the Enolates from alpha,beta-EPOXY Sulfoxides.4.Novel Asymmetric Synthesis Using Optical Active p-Tolylsulfinyl Group as a Chiral Auxiliary. (1)A Novel Synthesis of Chiral Epoxides and Allylic Alcohols. (2)The Practical Procedure of 1-Chloro-p-tolylsulfoxides and a Novel As Asymmetric Synthesis of (+)-Disparule and (-)-trans-Disparule. (3)A Novel Synthesis of (Z)-N-Arylaziridines.

1.生理活性萜的合成。(1)烯丙基硅烷化醛分子内环化合成eudsman - α -亚甲基-6,12-olide和-8,12-olide。(2)甲酰化烯酰卤化物分子内环合成α -亚甲基- γ -内酯的方法(3)生理活性戊二酚的合成：乙酸金樟醇、马兜铃醇-9-烯-3-醇和德尼醇-三冬苷和11-脱水- -三冬苷微生物转化的研究。(1)黑弧菌对三冬氨酸的微生物羟基化作用。(2)尼黑曲霉对11-脱氢桑托宁的微生物羟基化作用。环氧亚砜在有机合成中的应用(1)通过α， β -环氧亚砜合成α -取代羰基化合物、α， β -不饱和酮和碳同源羰基化合物酯的新方法。(2)镁盐诱导α， β -环氧亚砜开孔。-氯酮、-烷氧酮的合成。(3)基于羟基的开环环氧亚砜合成α -酰基、3-酮和螺环醚的新方法。(4) 1-氯烷基苯基亚砜和4-（苯基硫代）丁醛通过α， β -环氧亚砜立体选择性合成（E - 1-酰基丁二烯）。(5)基于分子内自由基环化的环氧亚砜环化新方法。(6)以α， β -环氧亚砜为原料合成醛醇及其烯醇酸酯的新方法。以光学活性对甲苯亚砜基为手性助剂的新型不对称合成。(1)手性环氧化合物和烯丙醇的新合成方法。(2) 1-氯-对甲基亚砜的实用合成方法及(+)-异戊二烯和(-)-反异戊二烯的不对称合成新方法。(3)一种新的(Z)- n -芳基嘧啶合成方法。

项目成果

T,Satoh: "A Novel Synthesis of 2-Acyl Cyclic Ethers and 3-Keto Cyclic Ethers Incuding Spiro Cyclic Ethers via Ring-opening α,β-Epoxy Sulfoxides by Hydroxyl Group"" Bull.Chem.Soc.Jpn. 61. 2109-2115 (1988)

T,Satoh：“通过羟基开环 α,β-环氧亚砜新型合成 2-酰基环醚和 3-酮环醚，包括螺环醚”” Bull.Chem.Soc.Jpn. 61. 2109 -2115 (1988)

T,Satoh: "Stereospecific Desulfination of Sulfinylaziri dines with Ethylmagnesium Bromide:A Novel Synthesis of(Z)-N-Arylaziridines." Tetrahedron Lett. 29. 4093-4096 (1988)

T,Satoh：“用乙基溴化镁对亚磺基氮丙啶进行立体定向脱硫：(Z)-N-芳基氮丙啶的新型合成。”

T.Satoh, T.Sato, T.Ohara, K.Yamakawa: "Stereospecific Desulfination of Sulfinlaziridines with Alkyl Metals: A Novel Synthesis Including Asymmetric Synthesis of (Z)-N-Arylaziridines and Some Mechanistic Study." J.Org.Chem., 54, 3973-3978(1989).

T.Satoh、T.Sato、T.Ohara、K.Yamakawa：“用烷基金属对 Sulfinlaziridines 进行立体定向脱硫：一种新颖的合成方法，包括 (Z)-N-Arylaziridines 的不对称合成和一些机理研究。”

T.Satoh: "Reduction of α-Keto Sulfoxides having Alkyl Group and Chlorine Atom on α-Carbon:A Synthesis of(E)-α,β-Epoxy Sulfoxides." Chem.Pharm.Bill.37. 184-186 (1989)

T. Satoh：“α-碳上具有烷基和氯原子的 α-酮亚砜的还原：(E)-α,β-环氧亚砜的合成。Chem.Pharm.Bill.37”。 ）

T.Satoh, K.Iwamoto, K.Yamakawa: ""Intramolecular Ring Closure of alpha, beta-Epoxy Sulfoxides with Hydroxyl Group: A Novel Synthesis of 2-Acyl Cyclic Ethers and 3-Keto Cyclic Ethers." Tetrahedron Lett., 28 (23), 2663-2606(1987).

T.Satoh、K.Iwamoto、K.Yamakawa：“带有羟基的 α、β-环氧亚砜的分子内闭环：2-酰基环醚和 3-酮环醚的新型合成。”Tetrahedron Lett.，28