Development of New Selective Organic Processes and Their Application to the Synthesis of Biologically-active Molecules

新型选择性有机工艺的发展及其在生物活性分子合成中的应用

• 批准号: 03403017
• 负责人: SUGINOME Hiroshi
• 金额: $ 20.8万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-03403017/
• 关键词: Photochemical reaction; Organic Synthesis; alkoxyl radicals; Electrochemical reaction; Radical reaction; Alkyl hypoiodites; Biologically-active natural products; Steroids; ラジカル反応; ストロイド; セスキテルペン合成; セスキテルペン; オキシム; カルボキシル化反応; 有機分子変換; 複素環化合物

New Photoadditions of quinones leading to heterocyclic quinones. -A one-step formation of heterocyclic quinones by a new regioselective [3+2] photoaddition of 2-hydroxy, 2-amino-, and 2-mercapto-1,4-naphthoquinones with a variety of alkenes, alkyns and naphthol was found. The new [3+2] photoaddition reaction was then applied to the synthesis of maturinone. New photoacylation and alkylation of 2-arylamino-, and 2-alkylaminonaphtho quinones were also devised.Development of new methods for the transformations based on selective fragmentation of alkoxyl radicals.-Several new methods were devised for the synthesis of bicyclo[5.4.0]undecane skeleton, lignans, phthalides, sesquiterpenes, and gamma- and delta-lactones based on selective beta-scission of alkoxyl radicals. These methods were successfully applied to the total synthesis of several terpenoids and lignans such as ((〕SY.+-.〔))-caryophyllene, ((〕SY.+-.〔))-isocaryophyllene, ((〕SY.+-.〔))-himachalene, ((〕SY.+-.〔))-recifeolide, ((〕SY.+-.〔 … More ))-eudesmin, ((〕SY.+-.〔))-piperitol, and ((〕SY.+-.〔))-yangambin.New Selective photochemical reactions of unsaturated cyclic ketone oximes. -New stereospecific photoaddition of methanol and photoisomerization involving stereospecific photoaddition of proton were found and the mechanisms of the processes were established on the basis of deuterium-labelling studies.New stereoselective synthesis of 2,5-disubstituted pyrrolidines by electrochimecal, anionic, or radical cyclization of species generated from delta-alkenylamines.-Anodic oxidation of lithium amides of 1-and/or 5-substituted N-methyl-delta-alkenylamines or the treatment of 1- or 1,5-disubstituted N-methyl-delta-alkenylamines with a catalytic amount of butyllithium gave cis-N-methyl-2,5-disubstituted pyrrolidines stereoselectively in good yields while the trans-N-alkyl-2- and/or 5-substituted pyrrolidines are stereoselectively formed in high yields by heating a solution of N-chloro-delta-alkenylamines. New total synthesis of (-)-N-methylanisomycin by the anodic cyclization of delta-alkenylamine was achieved.Other results-A new electrochemical preparation of reactive zinc metal and its application to the facile and efficient isoprenylation of aldehydes and ketones were devised. The method was then applied to the new synthesis of pheromones such as ipsenol and ipsdienol. Less

醌类的新光加成反应产生杂环醌类。发现了2-羟基、2-氨基和2-巯基-1，4-萘醌与各种烯烃、炔烃和萘酚的区域选择性[3 + 2]光加成一步生成杂环醌的新反应，并将该新反应应用于苦参素酮的合成。2-芳氨基-和2-烷氨基萘醌的光酰化和烷基化反应也被设计出来。发展了基于烷氧基自由基选择性断裂的新的转化方法。基于烷氧基自由基的选择性β-断裂，设计了几种新的合成双环[5.4.0]十一烷骨架、木脂素、苯酞、倍半萜以及γ-和δ-内酯的方法。这些方法已成功地应用于（（）SY.+-等萜类和木脂素类化合物的全合成。（））-香紫苏烯，（（）SY.+-.（））-异香芹烯，（）SY.（））-喜玛拉稀，（）SY.+-.（））-recifeetamine，（（）SY.+-.〔 ...更多信息 ））-桉叶结蛋白，（（）SY.（））-胡椒醇和（）SY.（））-yangambin.不饱和环酮肟的新的选择性光化学反应。在氘标记研究的基础上，发现了新的甲醇立体定向光加成反应和涉及质子立体定向光加成反应的光异构化反应，并建立了反应机理。通过δ-烯胺的电化学、阴离子或自由基环化反应，立体选择性地合成了2，5-二取代吡咯烷。1-和/或5-取代的N-甲基-δ-链烯基胺的氨基化锂的阳极氧化或用催化量的丁基锂处理1-或1，5-二取代的N-甲基-δ-链烯基胺得到顺式-N-甲基-2，5-二取代的吡咯烷，而反式-N-烷基-2-和/或5-取代的吡咯烷是通过加热N-氯-N-甲基吡咯烷的溶液以高产率立体选择性形成的。δ-烯基胺。本文报道了通过δ-烯胺的阳极环化全合成（-）-N-甲基茴香霉素的新方法，并设计了一种新的反应性锌金属的电化学制备方法及其在醛和酮的异戊二烯化反应中的应用。然后将该方法应用于信息素如ipsenol和ipsdienol的新合成。少

项目成果

H.Suginome: "One-Step Formation of Furo[3,2-c]quinolin-4(5H)-ones by a New Regioselective [2+3] Photoaddition of Methoxy-substituted 4-Hydroxyquinolin-2-ones with Alkenes" Tetrahedron Lett.32. 5115-5118 (1991)

H.Suginome：“通过新的区域选择性 [2 3] 甲氧基取代的 4-羟基喹啉-2-酮与烯烃的光加成一步形成呋喃[3,2-c]喹啉-4(5H)-酮”四面体

M.Tokuda: "Synthesis of Dimethyl Cycloalkane-1,2-dicarboxylates by Electrochemical Cyclization of Dimethyl-2,(ω-1)-Dibromoalkanedioates using a Copper Anode" Bull.Chem.Soc.Jpn.64. 2590-2592 (1991)

M. Tokuda：“使用铜阳极电化学环化二甲基-2,(ω-1)-二溴链烷二酸酯合成二甲基环烷-1,2-二羧酸酯”Bull.Chem.Soc.Jpn.64 (1991)。 ）

H.Suginome: "Photoinduced Molecular Transformations.Part 135.New Synthesis of Taiwanin C and Justicidin E based on a Radical Cascade Process involving β-Scission of Alkoxyl Radicals generated from 3-Aryl-...." J.Chem.Soc.Perkin Trans.1. 3111-3117 (1992)

H.Suginome：“光诱导分子转化。第 135 部分。基于涉及 3-芳基-生成的烷氧基自由基的 β-断裂的自由基级联过程，新合成 Taiin C 和 Justicidin E。”J.Chem.Soc。珀金译文1。3111-3117 (1992)

H.Suginome: "Efficient Formation of a Spirotetrahydrofuran Ring by the Ionic Cyclization of Bishomoallyl Tertiary Alcohol via their Hypoiodites" J.Chem.Soc.Perkin Trans.1. 2917-2923 (1992)

H.Suginome：“通过次碘酸盐通过双烯丙基叔醇的离子环化有效形成螺四氢呋喃环”J.Chem.Soc.Perkin Trans.1。

H.Suginome: "Photoinduced Molecular Transformations.Part 138.A New Route to Dibenzo[a,d]cycloalkanes and Their Naphtho-analogues via Ring Expansion of Benzocyclobutenols involving Selective β-Scission of ...." J.Chem.Soc.Perkin Trans.1. 825-829 (1993)

H.Suginome：“光诱导分子转化。第 138 部分。通过苯并环丁烯醇的扩环，涉及...的选择性 β-断裂，获得二苯并[a,d]环烷烃及其萘并类似物的新路线。”J.Chem.Soc。珀金翻译1。825-829（1993）