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One-Pot Synthesis of Aldehydes or Alcohols from CO2 via Formamides or Silyl Formates
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2023-02-28 , DOI: 10.1002/adsc.202300031
Fan Yang 1 , Yuta Saiki 1 , Koichi Nakaoka 1 , Tadashi Ema 1
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2023-02-28 , DOI: 10.1002/adsc.202300031
Fan Yang 1 , Yuta Saiki 1 , Koichi Nakaoka 1 , Tadashi Ema 1
Affiliation
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The solvent-free N-formylation of 2-(methylamino)pyridine with CO2 and phenylsilane was catalyzed by Cu(OAc)2 alone to give N-methyl-N-(2-pyridyl)formamide called Comins-Meyers formamide. The X-ray crystallographic analysis of a copper complex revealed a paddle-wheel structure consisting of two copper ions bridged by four acetate ions with two molecules of 2-(methylamino)pyridine on both axial sites, which suggested (i) the improved solubility of the copper ion and (ii) the enhanced nucleophilicity of the acetate ion for the activation of phenylsilane. 1H NMR spectra of benzene-d6 solutions containing Cu(OAc)2, 2-(methylamino)pyridine, and phenylsilane showed a singlet signal at 2.62 ppm, which was assigned to a catalytically active Cu−H species, and this signal disappeared upon exposure to CO2. Comins-Meyers formamide synthesized from 2-(methylamino)pyridine via the copper-catalyzed hydrosilylation of CO2 under solvent-free conditions was directly subjected to the Grignard reactions in THF for the one-pot synthesis of aldehydes or alcohols. On the other hand, silyl formates prepared from CO2 and phenylsilane using tetrabutylammonium acetate (TBAA) as an organocatalyst were also found to be good precursors of alcohols.
中文翻译：
通过甲酰胺或甲硅烷基酯一锅法从 CO2 合成醛或醇
2-(甲基氨基)吡啶与CO 2和苯基硅烷的无溶剂N-甲酰化仅由Cu(OAc) 2催化得到N-甲基-N- (2-吡啶基)甲酰胺，称为Comins-Meyers甲酰胺。铜络合物的 X 射线晶体学分析揭示了一个桨轮结构，该结构由两个铜离子组成，四个乙酸根离子在两个轴向位点上桥接两个 2-(甲基氨基) 吡啶分子，这表明 (i) 提高了溶解度铜离子和 (ii) 乙酸根离子增强的亲核性以激活苯基硅烷。含Cu(OAc) 2苯- d 6溶液的1 H NMR谱、2-(甲基氨基)吡啶和苯基硅烷在 2.62 ppm 处显示单线态信号，该信号归属于具有催化活性的 Cu-H 物质，并且该信号在暴露于 CO 2 时消失。将2-(甲基氨基)吡啶在无溶剂条件下通过铜催化的CO 2氢化硅烷化合成的Comins-Meyers甲酰胺直接在四氢呋喃中进行格氏反应，一锅法合成醛类或醇类。另一方面，还发现使用乙酸四丁基铵 (TBAA) 作为有机催化剂由 CO 2和苯基硅烷制备的甲硅烷基酯是良好的醇前体。
更新日期：2023-02-28
中文翻译：
通过甲酰胺或甲硅烷基酯一锅法从 CO2 合成醛或醇
2-(甲基氨基)吡啶与CO 2和苯基硅烷的无溶剂N-甲酰化仅由Cu(OAc) 2催化得到N-甲基-N- (2-吡啶基)甲酰胺，称为Comins-Meyers甲酰胺。铜络合物的 X 射线晶体学分析揭示了一个桨轮结构，该结构由两个铜离子组成，四个乙酸根离子在两个轴向位点上桥接两个 2-(甲基氨基) 吡啶分子，这表明 (i) 提高了溶解度铜离子和 (ii) 乙酸根离子增强的亲核性以激活苯基硅烷。含Cu(OAc) 2苯- d 6溶液的1 H NMR谱、2-(甲基氨基)吡啶和苯基硅烷在 2.62 ppm 处显示单线态信号，该信号归属于具有催化活性的 Cu-H 物质，并且该信号在暴露于 CO 2 时消失。将2-(甲基氨基)吡啶在无溶剂条件下通过铜催化的CO 2氢化硅烷化合成的Comins-Meyers甲酰胺直接在四氢呋喃中进行格氏反应，一锅法合成醛类或醇类。另一方面，还发现使用乙酸四丁基铵 (TBAA) 作为有机催化剂由 CO 2和苯基硅烷制备的甲硅烷基酯是良好的醇前体。
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