Synthesis of Highly Reactive Organometallic Compounds and its Application to Highly Selective Organic Synthesis

高活性有机金属化合物的合成及其在高选择性有机合成中的应用

• 批准号: 06453131
• 负责人: HOSOMI Akira
• 金额: $ 4.74万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453131/
• 关键词: 1,3-Dipolar; 1,3-Elimination; Carbonyl ylids; Reductive metalation; Allylcopper; Samarium-mediated reactions; [3+2] Cycloaddition; Silicon-directed cyclization; 立体選択的合成; 高選択的有機合成; [3+2]環化付加; フッ化セシウム; (シリルメチル)クロロメチルエーテル

The following results are obtained in this research project.1. Creation and Reactions of Carbonyl Ylides and Related 1,3-Dipolar Reagents1,3-Dipolar reagents are important and interesting chemical species from both synthetic and theoretical points of view. The novel findings that simple carbonyl ylides, otherwise inaccessible, were indeed expediently generated by the silicon-based 1,3-elimination from alpha-aryl-substituted chloromethyl trimethylsilylmethyl ether under mild and neutral conditions which provided the powerful one-step synthesis of dihydrofurans and tetrahydrofurans and related heterocylesvia [3+2] cycloadditions to a variety of multiple pi-bonds including C=C,C=C,C=O,C=S,C=N,N=N.2. Unprecedented Samarium-Mediated Reactions : Generation of Non-Stabilized Carbonyl YlidsSamarium reveals a strong reducing ability and by virue of this character together with its oxophilicity, is widely applied to organic synthesis in the formation of carbon-carbon bonds and transformation of … More a variety of functionalities with high selectivities. In the course of our study on the generation and reactions of reactive species, we report herein the generation of novel active species, nonstabilized carbonyl ylids from iodomethyl silyl ethers mediated by samarium, otherwise inaccessible, and their [3+2] cycloadditions to a variety of unsaturated compounds such as aldehydes, alkenes, allenes, and alkynes.3. Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using OrganocuprateKetene dithioacetals bearing a chlorine atom at an allylic position are cleanly reduced to generate the corresponding allylcopper reagents by treatment with two equimolar amounts of dimethylcuprate derived from cuprous cyanide (Me_2Cu (CN) Li_2). This reaction displays remarkable contrast to hitherto known reactions of cuprates in a sense of highly chemoselective reduction (only metal-halogen exchange reaction occurs) toward substitution reactions and is formally a new type of reaction for the generation of allylcopper species.4. Silicon-Directed Cyclization of Vinylsilanes Bearing Hydroxy Group Catalyzed by an AcidThe acid-catalyzed cyclization of vinylsilanes bearing a hydroxy group took place cleanly to give tetrahydrofurans and tetrahydropyans, and the addition of hydroxy group to vinylsilane proceeded in a syn stereoselective fashion. Less

在本研究项目中，取得了以下成果。羰基叶立德及其相关的1，3-偶极试剂的生成和反应1，3-偶极试剂无论从合成角度还是理论角度都是重要而有趣的化学物种。新的发现，简单的羰基叶立德，否则无法获得，确实是方便地通过硅基1，3-消除从α-芳基取代的氯甲基三甲基硅基甲醚在温和和中性条件下，提供了强大的一步合成二氢呋喃和四氢呋喃以及相关的杂芳烃通过[3+2]环加成到各种多个pi键，包括C=C，C=C，C=O，C=S，C=N，N=N.2。Sm介导的反应：生成不稳定的羰基Ylids-Sm具有很强的还原能力，加上它的亲氧性，被广泛应用于有机合成中碳-碳键的形成和…的转化更多种类的功能，具有高选择性。在我们对活性物种的生成和反应的研究过程中，我们在这里报道了由Sm介导的碘甲基硅基醚生成新的活性物种，非稳定的羰基叶立德，以及它们的[3+2]环加成到各种不饱和化合物上，如醛、烯、烯和炔。用一种新的有机铜还原反应直接生成和反应硫取代的烯丙基铜试剂用两种等摩尔量的氰化亚铜衍生的二甲基铜酸盐(Me_2Cu(CN)Li_2)处理烯丙基铜缩二硫缩醛，干净地还原生成相应的烯丙基铜试剂。与已知的铜酸盐反应相比，该反应具有很高的化学选择性还原(仅发生金属-卤素交换反应)，有利于取代反应，是一种新型的生成烯丙基铜物种的反应。含羟基乙烯基硅烷在酸催化下的硅定向环化反应生成四氢呋喃和四氢吡喃，羟基与乙烯基硅烷的加成反应以立体选择性的方式进行。较少

项目成果

M.Hojo, H.Harada, C.Murakami and A.Hosomi: "Direct Generation and Reactions of Sulfur-Substituted Allylcopper Reagents by a Novel Reduction Reaction Using Organocuprate" J.Chem.Soc., Chem.Commun.(23). 2687-2688 (1994)

M.Hojo、H.Harada、C.Murakami 和 A.Hosomi：“通过使用有机铜的新型还原反应直接生成硫取代的烯丙基铜试剂”J.Chem.Soc.、Chem.Commun.(23)。

Akira HOSOMI: "Cross-Coupling Reaction of Peutacoordinate Alkeuyfsilicates with Organic Halides and Triflates Catalyed by a Palladium Complex" Bull. Soc. Chim. France. 132. 499-508 (1995)

Akira HOSOMI：“钯配合物催化的长配位硅酸与有机卤化物和三氟甲磺酸酯的交叉偶联反应”公报。

Akira HOSOMI: "A Novel and Efficient Generation of Functionalized Vinylcopper Reagents and their Reactions with Electrophiles.Synthesis of β-Methylthiobutenolides" Chem.Lett.3. 437-440 (1994)

Akira HOSOMI：“功能化乙烯基铜试剂及其与亲电试剂的反应的新型高效生成。β-甲基硫代丁烯内酯的合成”Chem.Lett.3 (1994)。

Akira HOSOMI: "Reductive Cupration of α-Cyanoketenedithioacetals.Generation of Functionalized(E)-Vinylcopper Reagents and their Reactions with Electrophiles" Bull.Chem.Soc.Jpn.67. 1495-1498 (1994)

Akira HOSOMI：“α-氰基烯二硫缩醛的还原铜化。官能化 (E)-乙烯基铜试剂的生成及其与亲电子试剂的反应”Bull.Chem.Soc.Jpn.67 (1994)。

Akira HOSOMI: "Divergent Stereoselectivity in the Reduction of α,β-Epoxy Ketones Using Hydridosilicates" Tetrahedron Lett. 35(印刷中). (1994)

Akira HOSOMI：“使用氢化硅酸盐还原 α,β-环氧酮时的不同立体选择性”Tetrahedron Lett 35（出版中）。