New chiral sources for asymmetric synthesis

用于不对称合成的新手性来源

• 批准号: 08672428
• 负责人: SUEMUNE Hiroshi
• 金额: $ 1.41万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08672428/
• 关键词: asymmetric synthesis; enzymatic hydrolysis; asymmetric reaction; diol; optically active compound; 環変換; 環状ジオール; 炭素環ヌクレオシド; ヘリシティー

Following results were obtained through this project.1) Asymmetric induction into meso-1,3-diacetoxy-5-cycloheptene by PFL-catalyzed hydrolysis afforded monoacetate (1S,3R)-6 of 97% enantiomeric excess (e.e.), which was converted into a synthetic equivalent of delta-lactone moiety in mevinic acid derivatives.2) Asymmetric transesteriflcation of meso-spirodiol using Pseudomonas fluorescens lipase gave the corresponding monoacetate of high enantiomeric excess, from which the formal synthesis of (-) -curcumanolide A was achieved.3) Total synthesis of furoscrobiculin B,a lactarane sesquiterpene isolated from basidiomycetes of mushurooms, was achieved via an improved synthetic route of our previous work based on a Furan Ring Transfer reaction and base-catalyzed pinacol-type rearrangement.4) Pseudomonas fluorescens lipase-catalyzd asymmetric hydrolysis of meso-2,5-bis (acetoxymethyl) -3,4- (isopropylidenedioxy) tetrahydrofuran afforded the optically active correponding monoacetate of 92% e.e. in 94% yield. The absolute configuration was determined to be 2S,3S,4R,5R by chemical correlation with D-allose.5) Optically active 5-cyclooctene-1,2-diol derivatives prepared by enzymatic procedure have been converted into bicyclo [3.3.0] octane derivatives by transannular reaction with complete inversion of stereogenic center attached by a leaving group. Formal synthesis of (+) -iridomyrmecin has been achieved starting from (S,S) -5-cyclooctene-1,2-diol by using this process.

1）通过PFL催化水解不对称诱导生成meso-1，3-二乙酰氧基-5-环庚烯，得到对映体过量（e.e.）为97%的单乙酸酯（1 S，3R）-6，2）利用荧光假单胞菌脂肪酶对meso-spirobiol进行不对称反式异构化，得到相应的高对映体过量的单乙酸酯，并由此进行了（-）-姜黄素A的形式化合成。3）呋喃子菇素B的全合成，4）荧光假单胞菌脂肪酶催化meso-2，5-双（乙酰氧基甲基）-3，4-（亚异丙二氧基）四氢呋喃的不对称水解，得到光学活性的相应单乙酸酯，其e.e. 94%的收益5）酶法合成的光学活性5-环辛烯-1，2-二醇衍生物通过跨环反应，立体异构中心完全转化为双环[3.3.0]辛烷衍生物。以（S，S）-5-环辛烯-1，2-二醇为起始原料，用该方法合成了（+）-虹彩霉素。

项目成果

H.Kaku: "Asymmetric Synthesis of the δ-Lactone Moiety in Mevinic Acid Derivatives Using an Enzymatic Procedure" Tetrahedron:Asymmetry. 8. 195-201 (1997)

H.Kaku：“使用酶促程序不对称合成甲维酸衍生物中的 δ-内酯部分”Tetrahedron：Asymmetry 8. 195-201 (1997)。

T.Horikawa: "Synthesis of Optically Active Bicyclo[3.3.0]octance Skeleton Using Transannular Reaction" Chem.Pharm.Bull.46. 17-21 (1997)

T.Horikawa：“利用跨环反应合成光学活性双环[3.3.0]八烷骨架”Chem.Pharm.Bull.46。

M.Seki: "Total Synthesis of (dl) -Furoscrobiculin B" J.Chem.Soc, Perkin Transaction 1. 1707-1714 (1997)

M.Seki：“(dl)-Furoscrobiculin B 的全合成”J.Chem.Soc，Perkin Transaction 1. 1707-1714 (1997)

H.Kaku: "Asymmetric Synthesis of the delta-Lactone Moiety in Mevinic Acid Derivatives Using an Enzymatic Procedure." Tetrahedron : Asymmetry. 8. 195-201 (1997)

H.Kaku：“使用酶法不对称合成甲维酸衍生物中的 δ-内酯部分。”

T.Fujita: "Enantioselective Synthesis of (-) -Curcumanolide A Using Enzymatic Transesterification of meso-Spirodiol." J.Org.Chem.62. 3824-3830 (1997)

T.Fujita：“利用内消旋螺二醇的酶促酯交换反应对映选择性合成 (-)-Curcumanolide A”。