Study on Asymmetric Synthesis and Application to physiological Active Compound

生理活性化合物的不对称合成及应用研究

• 批准号: 03671016
• 负责人: YAMAKAWA Koji
• 金额: $ 0.45万
• 依托单位: Science University of Tokyo, Faculty of Pharmaceutical Sciences
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03671016/
• 关键词: asymmetric synthesis; new methodology; diastereoselective cyclization; radical cyclization; phenyl sulfoxides; terepenes; cembranes; alpha-methylene-gamma-lactones; 不斉合成; 新方法; ジアステレオ選択的閉環反応; ラジカル閉環反応; フェニルスルホキシド; テルペン; センブラン類; α-メチレン-γ-ラクトン

1. Asymmetric Synthesis of Some Carbonyl Compounds Using 1-Chloroalkyl p-Tolyl Sulfoxides. Practical synthetic procedure of optical active 1-chloroalkyl p-tolyl sulfoxides was investigated, and asymmetric synthesis of optical active epoxides, allylic alcohols, amino-aldehydes, and aziridines had been sucseccful.(1) Asymmetric synthesis of alpha-hydroxy-carboxylic acids, esters, amides, acetylenes, propargylic alcohols starting from the optical active 1-chloroalkyl p-tolyl sulfoxides were successful.(2) Synthesis of optical active amido compounds by the asymmetric Favorskii rearrangement was investigated.(3) Synthesis of methylenecyclopropane spiro linked with cycloalkanes via cyclization of allylic epoxides was investigated, its application to a sythesis of fused rings 3-methylfuranes.2. Diastereoselective cyclization of omega-formylated allylic silanes into bicyclic alpha-methylene-gamma-lactones.(1) Diastereoselective cyclization of omega-formylated allylic silanes using chiral auxiliary groups was investigated.(2) Diastereoselective sythesis of cis and trans-p-methanolides starting from (+)-citronellal was sucessful.(3) Total synthesis of cembrenolide, marine natural product, was successful.

1.用1-氯烷基对甲苯基亚砜不对称合成羰基化合物研究了光学活性1-氯烷基对甲苯基亚砜的合成工艺，成功地合成了光学活性环氧化合物、烯丙醇、氨基醛和氮杂环丙烷。(1)以光学活性的1-氯烷基对甲苯基亚砜为原料，成功地进行了α-羟基羧酸、酯、酰胺、炔、炔丙醇的不对称合成。(2)研究了利用不对称Favorskii重排反应合成光学活性酰胺化合物。(3)研究了烯丙基环氧化物环化合成亚甲基环丙烷螺环连接环烷烃的方法，并将其应用于稠环3-甲基呋喃的合成.ω-甲酰化烯丙基硅烷非对映选择性环化为双环α-亚甲基-γ-内酯。(1)研究了ω-甲酰化烯丙基硅烷与手性辅助基团的非对映选择性环化反应。(2)以（+）-香茅醛为起始原料，非对映选择性合成了顺式和反式-对-甲醇内酯。(3)成功地全合成了海洋天然产物西布仑特。

项目成果

T.Satoh: " -Sulfinylcarbenoids:Homologation of ketones to -sulfi nyl ketones using chloromethyl phenyl sulfoxides as a one carbon homologating agents." Tetrahedron Lett.,. 33. 7181- (1992)

T.Satoh：“-亚磺酰基碳烯：使用氯甲基苯基亚砜作为一碳同系剂将酮同系为 -亚磺酰基酮。”

K.Nishitani: "Diastercoselective cyclization of ω-formylated allyl silanes into bicyclic α-methylene-γ-butyrolactones: A facile sythesis of p-mentanolides." Heterocycles. 33. 97 (1992)

K.Nishitani：“ω-甲酰化烯丙基硅烷的双酯共选择性环化成双环 α-亚甲基-γ-丁内酯：对-薄荷醇内酯的简便合成”33. 97 (1992)。

T.Satoh: "A novel synthesis of Methylenecyclopropane SpiroーLinked with Cycloalkanes via a Cyclization of Allylic Epoxides and Its Application to a Synthe sis of Fused 3ーMethylfurans." Bull.Chem.Soc.Jpn.64. 1129-1135 (1991)

T.Satoh：“通过烯丙基环氧化物环化与环烷烃连接的亚甲基环丙烷及其在稠合 3-甲基呋喃合成中的应用”Bull.Chem.Soc.Jpn.64 (1991)。

T.Satoh: "Ethylmagnesium Brimide Mediated Desulfinylation of αーHaloーβーketofuloxides Giving αーHaloketones,and Trapping of the Magnesium Enolated Intermedi ate." Tetrahedron Lett.32. 5599-5600 (1991)

T. Satoh：“乙基溴化镁介导的 α-卤代-β-酮氟氧化物脱硫酰化，生成 α-卤代酮，并捕获烯醇化镁中间体。”32 (1991)。

T.Satoh, K.Onda, k. Yamakawa: "1-Chloroalkyl p-tolyl sulfoxides as useful agent for homologation of carbonyl compounds to alpha-hydroxy acids, esters, amides and alpha,alpha'-dihydroxy ketones" J.Org. Chem. 56. 4129 (1991)

T.Satoh，K.Onda，k。