Development of Efficient Molecular Transformations Using Metal and Heteroatom Compounds

利用金属和杂原子化合物开发高效分子转化

• 批准号: 14550822
• 负责人: SEGI Masahito
• 金额: $ 1.92万
• 依托单位: Kanazawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14550822/
• 关键词: Homopropargyl selenide; Propargyl selenide; Hydrozirconation; Stille-type coupling; Selenoxide elimination; [2,3] Sigmatropic rearrangement; Polyene compound; Allenyl alcohol; フェニルプロパルギルセレニド; 末端アルキン水素; α,β-不飽和アシルシラン; ジアニオン; 2,5-ジヒドロフラン; 分子内ヘミ

Terminal alkynes having a PhSe group on a or β carbon atom contain some reactive sites (C-C triple bond, acidic protons, phenylseleno group) and has potential as a synthetic precursor to highly functionalized compounds. Hydrozirconation of homopropargyl phenyl selenide (1)with Schwartz's reagent gave the corresponding terminal vinylzirconocene regio-and stereoselectively. This zirconocene intermediate was successively subjected to Stille-type coupling with aryl or alkenyl iodides in the presence of Pd(0) catalyst, followed by oxidative removal of the phenylseleno group via selenoxide syn elimination to afford conjugated polyene compounds with E-configuration in good yields. Phenyl propargyl selenide (2)was easily deprotonated by 2 equiv of LDA in THF at -78℃ to give a solution of the dianion reagent. Aldehydes reacted with the dianion exclusively at the a position of selenium atom to afford homopropargyl alcohol derivatives. Oxidation of these compounds with 1 equiv of m-CPBA gave the … More corresponding selenoxides, which underwent the [2,3] sigmatropic rearrangment to yield α-phenylseleno-substituted enone derivatives, presumably via allenyl alcohol intermediates. E-isomers of enone compounds were followed by cyclization via an intramolecular hemiacetalization to give 2-hydroxy-2,5-dihydrofuran derivatives. Interestingly, the addition of pyridine to the reaction mixture led to an exclusive formation of the dihydrofuran compounds. Thus, the dianion of 2 served as a synthetic equivalent of acrolein dianion, and the two anionic centers can be utilized separately. The similar oxidation of silylated propargyl selenide derivatives resulted in the formation of α,β-unsaturated acylsilanes in good yields. Silylated homopropargyl alcohol derivatives were oxidized by m-CPBA to give 2-silyl-3-phenylselenofuran compounds and γ-hydroxy-substituted Z-α,β-unsaturated acylsilanes. The former may be obtained via an intramolecular cyclization of the corresponding E-α,β-unsaturated acylsilanes followed by the dehydration. Less

末端炔在碳原子或碳β原子上有一个se基团，含有一些活性位点（C-C三键、酸性质子、苯基硒基），有潜力作为高功能化化合物的合成前体。用施瓦兹试剂对同丙炔苯硒化物(1)进行氢锆化反应，得到了相应的端乙烯基锆新世区和立体选择性。该新锆中间体在Pd(0)催化剂的存在下，与芳基或烯基碘化物进行stille型偶联，然后通过硒氧化物同步消除氧化去除苯基硒基，得到收率高的e-构型共轭多烯化合物。苯基丙炔硒化物(2)在-78℃的四氢呋喃中，用2等量的LDA很容易去质子化，得到离子试剂溶液。醛只在硒原子的一个位置上与离子反应，生成同丙炔醇衍生物。这些化合物与1等量的m-CPBA氧化得到更多相应的硒氧化物，这些硒氧化物经过[2,3]异位重排生成α-苯基硒取代烯酮衍生物，可能是通过烯醇中间体产生的。烯酮化合物的e -异构体随后通过分子内半乙酰化环化得到2-羟基-2,5-二氢呋喃衍生物。有趣的是，在反应混合物中加入吡啶会导致只生成二氢呋喃化合物。因此，2的阴离子作为丙烯醛的合成物，两个阴离子中心可以分别利用。硅基化丙炔硒化物衍生物的类似氧化反应生成了收率较高的α，β-不饱和酰基硅烷。硅基化同丙炔醇衍生物经m-CPBA氧化得到2-硅基-3-苯基硒化呋喃化合物和γ-羟基取代的Z-α，β-不饱和酰基硅烷。前者可以通过相应的E-α，β-不饱和酰基硅烷的分子内环化，然后脱水得到。少

项目成果

Masahito Segi: "Synthetic Transformations to Unsaturated Compounds Using Homopropargylic Selenide Derivatives"Tetrahedron Letters. (in press).

Masahito Segi：“使用均炔丙基硒化物衍生物合成转化为不饱和化合物”四面体字母。

Mitsunori Honda: "Diastereoselective Alkylation and Reduction of β-Alkoxyacylsilanes : Stereoselective Construction of Three Contiguous Stereogenic Centers"Tetrahedron. 59. 8203-8212 (2003)

Mitsunori Honda：“β-烷氧基酰基硅烷的非对映选择性烷基化和还原：三个连续立体中心的立体选择性构建”四面体。 59. 8203-8212 (2003)

Aojia Zhou: "The Reaction of Selenoaldehydes with 2-Methoxyfuran Using Their Generation by Retro Diels-Alder Reaction"Tetrahedron Letters. 44・6. 1179-1182 (2003)

周敖嘉：“利用逆狄尔斯-阿尔德反应生成硒醛与 2-甲氧基呋喃的反应”四面体快报 44・6 (2003)。

Aojia Zhou: "The Reaction of Selenoaldehydes with 2-Methoxyfuran Using Their Generation by Retro Diels-Alder Reaction"Tetrahedron Letters. 44. 1179-1182 (2003)

周敖嘉：“利用逆狄尔斯-阿尔德反应生成硒醛与 2-甲氧基呋喃的反应”四面体字母。

Masahito Segi: "Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of PhSe-Substituted Vinylzirconates"Tetrahedron Letters. (発表予定).

Masahito Segi：“通过 PhSe 取代的乙烯基锆酸盐的金属转移生成乙烯基有机铜酸盐的共轭加成”四面体快报（待出版）。