Stereoselective synthesis of terminal conjugated enynes using alkenylboron compounds

使用烯基硼化合物立体选择性合成末端共轭烯炔

• 批准号: 13650898
• 负责人: HOSHI Masayuki
• 金额: $ 2.3万
• 依托单位: Kitami Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650898/
• 关键词: alkenyldialkylborane; 2-bromo-1-(trimethylsilyl)acetylene; cross-coupling; copper(II) acetylacetonate; 3-alken-1-yne; 1-trimethylsilyl-3-alken-1-yne; Sonogashira reaction; 1-aryl-3-alken-1-yne; アルケニルボラン; 2-ブロモート(トリメチルシリル)アセチレン

We have studied the copper(II) acetylacetonate-catalyzed cross-coupling reaction of (E)- and (Z)-1-alkenyldialkylborane with 2-bromo-1-(trimethylsilyl)acetylene and the application of the cross-coupled products, (E)- and (Z)-3-alken-1-yne, to Sonogashira reaction. The results are as follows:1. By using NaOMe (1M solution in methanol) as a base, the cross-coupling reaction as well as protodesilation proceeded simultaneously under very mild conditions, at -15 ℃ to room temperature, to provide (E)- and (Z)-3-alken-1-ynes in good yields with high regio- and stereoselectivities.2. By using LiOH・H_2O as a base, the cross-coupling reaction proceeded with practically no protodesilation under the same conditions to afford (E)- and (Z)-l-trimethylsilyl-3-alken-1-ynes in moderate to good yields with high regio- and stereoselectivities.3. Both (E)- and (Z)-3-alken-1-yne, in situ generated by the copper(II) acetylacetonate-catalyzed cross-coupling reaction, were subjected to the reaction with aryl iodide in a one-pot manner, and hence the reaction proceeded at room temperature in the presence of PdCl_2(PPh_3)_4-CuI as catalyst and tetrabutylammonium hydroxide as base to give the corresponding arylated conjugated enynes in high yields with high regio- and stereoselectivities.

本文研究了乙酰丙酮铜（Ⅱ）催化的（E）-和（Z）-1-烯基二烷基硼烷与2-溴-1-（三甲基硅基）乙炔的交叉偶联反应，以及交叉偶联产物（E）-和（Z）-3-阿尔肯-1-炔在Sonogashira反应中的应用。研究结果如下：1.以NaOMe（1 M甲醇溶液）为碱，在-15 ℃至室温的温和条件下，进行交叉偶联反应和脱硅反应，以高产率得到（E）-和（Z）-3-阿尔肯-1-炔，并具有较高的区域和立体选择性.以LiOH·H_2O为碱，在相同的条件下，几乎不发生脱硅反应，就可以得到（E）-和（Z）-1-三甲基硅基-3-阿尔肯-1-炔，产率中等，且具有较高的区域和立体选择性.通过乙酰丙酮铜（II）催化的交叉偶联反应原位生成的（E）-和（Z）-3-阿尔肯-1-炔都以一锅法与芳基碘反应，在PdCl_2（PPh_3）_4-存在下，反应在室温下进行以CuI为催化剂，四丁基氢氧化铵为碱，以高产率和高的区域选择性和立体选择性合成了相应的芳基化共轭烯炔。

项目成果

Masayuki Hoshi: "Construction of terminal conjugated enynes: Regio- and stereoselective syntheses of 3-alken-1-ynes and 1-trimethylsilyl-3-alken-1-ynes from alkenyldialkylboranes and (trimethylsilyl)ethynyl bromide"Synlett. 1101-1104 (2002)

Masayuki Hoshi：“末端共轭烯炔的构建：从烯基二烷基硼烷和（三甲基甲硅烷基）乙炔基溴中区域选择性和立体选择性合成 3-烯基-1-炔和 1-三甲基甲硅烷基-3-烯-1-炔”Synlett。

M.Hoshi, K.Shirakawa: "Construction of terminal conjugated enynes : Regio-and stereoselective syntheses of 3-alken-1-ynes and 1-trimethylsilyl-3-alken-1-ynes from alkenyldialkylboranes and (trimethylsilyl) ethynyl bromide"Synlett. 1101-1104 (2002)

M.Hoshi、K.Shirakawa：“末端共轭烯炔的构建：从烯基二烷基硼烷和（三甲基甲硅烷基）乙炔基溴中区域选择性合成 3-烯-1-炔和 1-三甲基甲硅烷基-3-烯-1-炔”Synlett

M.Hoshi, K.Shirakawa: "Construction of terminal conjugated enynes : Regio-and stereoselective syntheses of 3-alken-1-ynes and 1-trimethylsilyl-3-alken-1-ynes from alkenyldialkylboranes and (trimethylsilyl) ethynyl bromide"Synlett. No.7. 1101-1104 (2002)

M.Hoshi、K.Shirakawa：“末端共轭烯炔的构建：从烯基二烷基硼烷和（三甲基甲硅烷基）乙炔基溴中区域选择性合成 3-烯-1-炔和 1-三甲基甲硅烷基-3-烯-1-炔”Synlett