New Organic Synthesis based on Photo- and Electrochemical Reactions involving Intramolecular Rearrangements.

基于涉及分子内重排的光化学反应和电化学反应的新型有机合成。

• 批准号: 61470091
• 负责人: SUGINOME Hiroshi
• 金额: $ 4.03万
• 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 (B)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-61470091/
• 关键词: photochemical reactions; electro-organic synthesis; steroids; alkoxyl radicals; -scission; photo-rearrangements; macrocyclic ketones; 大環状ケトン; 分子内光転位反応; アルコキシルラジカル; ピロリジン合成; 有機合成; ラジカル反応; 転位反応; 分子変換

1. A conformational dependence of [1,3] sigmatropic photo-rearrangements in , -unsaturated ketones was found by the study of the photolysis of two steroidal 7-membered , -unsaturated ketones.2. The two new stereospecific rearrangements of excited steroidal oximes were found and mechanisms, which accommodate the stereospecificity of these photo-rearrangements proved by deuterium labelling studies, were proposed.3. New mothed was devised for two carbon ring expansions of 5- and 6-membered rings of -indanone and - tetralone through the [2+2] photocycloaddition of the enol ethers of the cyclic ketones followed by the radical cleavage of the fused bond of benzohomotropones through [2+2] photocycloaddition of 1- and 2-naphthols with methyl acrylate followed by a -scission of alkoxyl radicals derived from the adducts was also achieved.4. The photochemistries of cyclic -nitro ketones, 6-membered cyclic , '-dinitro ketones, and cyclic -nitro enones were studied and new photochemical processes of nitro compounds were found.5. New method was devised on the synthesis of several furanocoumarins and furano quinolones based on the [2+2] photocycloaddition- -scission sequence.6. Stereo-and regioselective synthesis of cis-1-alky1-2,5-disubstituted pyrrolidines by cyclization of aminyl radicals generated by anodic oxidation of lithium alkenylamides was devised.7. A simple new general synthesis of marocyclic ketones based on a three-carbon annelation of cyclic ketones followed by the regioselective radical cleavage of the fused bond of the resulting bicyclic systems was devised. New synthesis of 15-membered cyclic ketones, exaltone and ( )-muscone, were achieved by this method.

1.通过对两种甾体7元β-不饱和酮光解的研究，发现β-不饱和酮中[1,3]σ光重排具有构象依赖性。2．发现了激发甾体肟的两种新的立体特异性重排，并提出了通过氘标记研究证明的适应这些光重排立体特异性的机制。 3．设计了新方法，通过环酮烯醇醚的 [2+2] 光环加成，然后通过 1- 和 2-萘酚与丙烯酸甲酯的 [2+2] 光环加成，苯并同环酮的稠合键发生自由基断裂，从而实现 -茚满酮和 - 四氢萘酮的 5 元和 6 元环的两个碳环扩展。 还实现了由加合物衍生的烷氧基的α-断裂。4．研究了环硝基酮、六元环、'-二硝基酮、环硝基烯酮的光化学，发现了硝基化合物的新光化学过程。 5．提出了基于[2+2]光环加成--断裂序列合成多种呋喃香豆素类和呋喃喹诺酮类药物的新方法。 6．设计了利用烯基酰胺锂阳极氧化产生的氨基自由基环化立体和区域选择性合成顺式1-烷基1-2,5-二取代吡咯烷的方法。 7．设计了一种简单的新的大环酮通用合成方法，其基于环酮的三碳稠合，然后对所得双环系统的稠合键进行区域选择性自由基裂解。该方法实现了15元环酮、外旋酮和( )-muscone的新合成。

项目成果

H. Suginome,; H. Washiyama; S. Yamada.: "The Transformation of Cyclic Alcohols into Cyclic Acetals though a New Oxygen Atom Insertion by Photolysis in the Presence of Lead Tetraacetate and Iodine" Bull. Chem. Soc. Jpn.60. 1071-1083 (1987)

H.杉野，；

H. Suginome,; M. Kaji,; S. Yamada.: "Photo-induced Molecular Transformations. Part87. Regiospecific Photo-Beckmann Rearrangement of Steroidal , -Unsaturated Ketone Oximes: Synthesis of some Steroidal Enamio Lactams" J. Chem. Soc., Perkin Trans. 1,.

H.杉野，；

H. Suginome,; M. Itoh,; K. Kobayashi.: "Photoinduced Molecular Transformations. Part 88. Ring Expansion through [2+2] photocycloaddition- -Scission seguences: Synthesis of Benzohomo-tropones from 1- and 2-Naphtols and Methyl Acryiate" J. Chem. Soc., Perki

H.杉野，；

Masao Tokuda: Tetrahedron. 43. 281-296 (1987)

德田正夫：四面体。

M.Tokuda.: "Recent Advances in Electroorganic Synthesis", Proceeding of the Ist International Symposium on Electroorganic Synthesis. 113-116 (1987)

M.Tokuda.：“有机电合成的最新进展”，第一届国际有机电合成研讨会论文集。