Dynamic Sterocontrol of Unstable Organic Reacitve Species

不稳定有机反应物质的动态立体控制

• 批准号: 10208102
• 负责人: HOSOMI Akira
• 金额: $ 1.73万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208102/
• 关键词: Unstable Reactive Species; Stereoselective synthesis; Transition metal-catalyzed reactions; Redox systems; Srereocontrol; Samarium-mediated reactions; [3+2] Cycloaddition; Electron transfer process

The following various successful results were ottained during this study between 1998-2001.Symposiums are held at Sapporo in 1999 and Tsukuba in 2000.1. Silicon-directed Cyclization of Vinylysilanes : Stereoselective Synthesis of Tetrahydrofurans and TetrahydropyransSilicon-directed stereoselective syn addition of hydroxy group to olefinic double bond occurs intramolecularly in an acid-catalyzed cyclization of vinylsilanes bearing hydroxy group. The cyclization proceeds by stereospecific syn addition of the hydroxy group. Vinylsilanes, (Z)-5-silyl-4-penten-1-ols bearing a substituent on the methylene tether, smoothly undergo the acid-catalyzed cyclization to give trans-2,5-, cis-2,4-, and trans-2,3-disubstituted tetrahydrofurans, respectively, with moderate to high stereoselectivity.2. New Synthetic Reactions induced by the Redox Systems including Transition Metals directed to Stereocontrol3. Stereocontrol in the Transition Metal-Catalyzed Synthetic Reactions4. Unprecedented Manganese- … More Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsActivated manganese generates nonstabilized carbonyl ylides from bis(chloromethyl) ethers as a precursor, and using this system with manganese as a reductant, the reactions of the ylides with electron-deficient dipolarophiles can be attained without the direct reduction of dipolarophiles by the reductant.5. Manganese Ate Species : Generation and Reactions with ElectrophilesTrialkylmanganese(II) ate reagents, "R_3MnLi" reacted with iodomethylsulfides to produce thiomethylmanganese reagents, where the manganate serves as a reductant not an alkylation agent. The reductive behavior of trialkylmanganese(II) ate reagents provides a protocol for the direct generation of a new class of reagents, thiomethylmanganese reagents with structural variety, and the generated thiomethylmanganese reagents reacted with allyl bromides, enones and aldehydes.6. Sterocontrol in the radical Reactions7. Dynamic control of the reaction pathways in the Formation Reactions of Carbon-Carbon Bonds and Carbon-Silicon Bonds via Electron Transfer Process Less

在1998 - 2001年之间的研究期间，以下各种成功的结果是在1999年和Tsukuba举行的，并于2000.1举行。带有羟基的乙烯基硅烷的酸催化的环烷基含羟基的乙烯基含量。 trans-2,5- cis-2,4，具有中等至高的立体选择性非稳定的羰基YLIDSTIPTIPATICATIPATINALE的锰会从Bis（氯甲基）醚中作为前体产生非稳定的羰基，并将锰作为锰作为培养基降低偶极性载体。 （ii）直接生成具有结构性品种的反试剂剂的试剂方案，以及产生的硫甲基甲虫与烯丙基溴化物，烯烃和醛反应的反应。6和碳 - 硅转移ESS少

项目成果

A. Ogawa, M. Doi, I. Ogawa, and T. Hirao: "Highly Selective Three-Component Coupling of Ethyl Propionate, Alkenes, and DiphenylDiselenide under Visible-Light Irradiation"Angew. Chem. Int. Ed.. 38. 2027-2029 (1999)

A. Okawa、M. Doi、I. Okawa 和 T. Hirao：“可见光照射下丙酸乙酯、烯烃和二苯基二硒化物的高度选择性三组分偶联”Angew。

C. Toratsu, T. Fujii, T. Suzuki, K. Takai: "Cross Coupling Reactions between α,β-Unsaturated Ketones and Aldehydes with CrCl_2 : Aldol Condensation and Cyclopropanol Formation"Angew. Chem. Int. Ed.. 39. 2725-2727 (2000)

C. Toratsu、T. Fujii、T. Suzuki、K. Takai：“α,β-不饱和酮和醛与 CrCl_2 之间的交叉偶联反应：羟醛缩合和环丙醇形成”Angew Chem. 39。 -2727 (2000)

M. Tobisu, N. Chatani, T. Asaumi, K. Amako, Y. Ie, Y. Fukumoto, and S. Murai: "Ruthenium Carbonyl-Catalyzed [2 + 2 + 1]Cycloaddition of Ketones, Olefins, and Carbon Leading to Functionalized γ-Butyrolactones"J. Am. Chem. Soc.. 121(30). 7160-7161 (1999)

M. Tobisu、N. Chatani、T. Asaumi、K. Amako、Y. Ie、Y. Fukumoto 和 S. Murai：“钌羰基催化的 [2 + 2 + 1] 酮、烯烃和碳主导的环加成反应功能化 γ-丁内酯”J. Am. Chem. Soc.. 121(30). 7160-7161 (1999)

Hajime Ito, Tatsuki Yajima, Jun-ichi Tateiwa, and Akira Hosomi: "First Gold Complex-Catalysed Selective Hydrosilylation of Organic Compounds"Chem. Commun.. (11). 981-982 (2000)

Hajime Ito、Tatsuki Yajima、Jun-ichi Tateiwa 和​​ Akira Hosomi：“第一个金配合物催化有机化合物的选择性氢化硅烷化”Chem。

K.Takai: "Three-Component Coupling Reactions of Alkyl Iodides,1,3-Dienes,and Carbonyl Compounds by Sequential Generation of Radical and Anionic Species with CrCl2"Angew.Chem.Int.Ed. 37・8. 152-155 (1998)

K.Takai：“烷基碘、1,3-二烯和羰基化合物与 CrCl2 连续生成自由基和阴离子物种的三组分偶联反应”Angew.Chem.Int.Ed 37・8。 1998）