DEVELOPMENT OF HIGHLY EFFICIENT BENZYNE TRANSFORMATION PROCESS USING HYPERVALENT IODINE COMPOUNDS

利用高价碘化合物开发高效苯转化工艺

• 批准号: 07804046
• 负责人: KITAMURA Tsugio
• 金额: $ 1.47万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07804046/
• 关键词: Hypervalent Iodine Compounds; Benzyne; Iodonium Salts

We have prepared a new type of hypervalent iodine reagent, [o-(trimethylsilyl) phenyl] iodonium triflates, which bear a hyperleaving phenyliodonio group and a readily cleavable silyl group, and developed a highly efficient benzyne transformation process.(1) The benzyne precursor, [o-(trimethylsilyl) phenyl] iodonium triflate, was prepared by using highly reactive hypervalent iodine reagents developed by us.(2) Benzyne was readily generated in situ under very mild conditions by using Bu_4NF and KF.(3) The generated benzyne as above was quantitatively trapped by furan, isobenzofuran, anthracene, cyclopentadienone, and so on. This reaction provides a highly efficient benzyne transformation process.(4) Since the present reagent can be utilized under neutral conditions and at room temperature, it can be applied to the reactions with unstable azides and thiobenzophenones.(5) Substituted benzyne precursors were prepared and investigated in order to find the utility.

我们合成了一种新型的高价碘试剂[o-（三甲基硅基）苯基]碘鎓三氟甲磺酸盐，它带有一个超离去的苯基碘鎓和一个易断裂的硅基，并发展了一种高效的苯炔转化过程。(1)用我们研制的高活性高价碘试剂合成了苯炔前体[邻三甲基硅基苯基]碘鎓三氟甲磺酸盐。(2)用Bu_4NF和KF在非常温和的条件下容易地原位生成苄基。(3)上述生成的苯炔被呋喃、异苯并呋喃、蒽、环己烯酮等定量捕获，该反应提供了高效的苯炔转化过程。(4)由于本试剂可在中性和室温下使用，因此可用于与不稳定叠氮化物和硫代二苯甲酮的反应。(5)为了发现其实用性，制备并研究了取代苯炔前体。

项目成果

北村二雄 他6名: "Alkenyl-and Alkynyl-Substituted (p-Phenylene) bisiodonium Ditriflates by Reactions of a (p-Phenylene) bisiodine (III) Reagent with Alkynes and 1-Trimethylsilyl-1-alkynes" Bulletin of the Chemical Society of Japan. 68. 3637-3641 (1995)

Shio Kitamura 等 6 人：“烯基和炔基取代的（对亚苯基）二碘鎓二三氟甲磺酸盐通过（对亚苯基）二碘 (III) 试剂与炔烃和 1-三甲基甲硅烷基-1-炔烃的反应”化学会通报日本。68。3637-3641（1995）

北村二雄: "高反応性有機ヨウ素(III)反応剤の開発" 有機合成化学協会誌. 53. 893-905 (1995)

Futoshi Kitamura：“高活性有机碘 (III) 反应物的开发”有机合成化学学会杂志 53. 893-905 (1995)。

北村二雄: "Self-condensation of Iodosylbenzene. Formation of a p-Phenylene-type of Bisiodine (III) Reagents" Tetrahedron. 51. 6229-6236 (1995)

Futoshi Kitamura：“碘酰苯的自缩合。对亚苯基型双碘 (III) 试剂的形成”四面体 51。6229-6236 (1995)

北村二雄: "Synthesis of Novel Vinylbenziodoxolones from Alkynyl (o-carboxyphenyl) iodonium Salts" Synlett. 659-660 (1996)

Futoshi Kitamura：“从炔基（邻羧基苯基）碘鎓盐合成新型乙烯基苯并酮”Synlett 659-660（1996）。

北村二雄: "A New Route to Chiral Diaryldiacetylenic Liquid Crystals.Preparation of Iodonium Salts Bearing Chiral Alkynyl Ligands and Utility for Chiral Alkynyl Transfer Agents" Journal of American Chemical Society. (印刷中). (1997)

Futoshi Kitamura：“手性二芳基二乙炔液晶的新路线。带有手性炔基配体的碘鎓盐的制备和手性炔基转移剂的实用性”美国化学会杂志（1997 年）。