胺N-氧化物的新反应方式:用 (IV) 和 (IV) 双 () 复合物激活C-H
Jaime A Pool1, Brian L Scott, Jaqueline L Kiplinger
1Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA.
Journal of the American Chemical Society
|February 3, 2005
概括
和复合物激活二氧化物中的C-H键,形成新的循环金属化化合物. 这一发现揭示了actinide化学和pyridine N-oxides的新反应模式.
科学领域:
- 有机金属化学 有机金属化学
- 动因化物化学 动因化物化学
- 有机合成 有机合成
背景情况:
- 化N-氧化物通常会与金属复合体进行氧原子转移.
- 乙胺复合物以其独特的电子特性和反应性而闻名.
研究的目的:
- 研究 (IV) 和 (IV) 双 () 复合物的C-H激活能力.
- 为了探索新型的反应模式的pyridine N-氧化物与actinide中心.
主要方法:
- (IV) 和 (IV) 二氧化 (基) 复合物的合成: (C5Me5) 2AnR2 (An = U, Th; R = CH3, CH2Ph).
- 这些复合物的反应与 N-氧化和 N-氧化.
- 使用光谱技术对产生的循环金属产品进行表征.
主要成果:
- (IV) 和 (IV) 复合物成功地激活了二氧化物N-氧化物中的sp2和sp3C-H键.
- 形成罕见的环金属复合物: (C5Me5) 2An (R) [eta2- (O,C) -ONC5H4]和 (C5Me5) 2An (R) [eta2- (O,C) -ON-2-CH2-5-CH3-C5H3].
- 通过乙化金属中心介导的C-H激活的演示,与氧原子转移不同.
结论:
- 乙胺 bis (((alkyl) 复合物表现出前所未有的C-H激活反应性与胺 N-氧化物.
- 这项研究在有机金属化学中为二烯N-氧化物建立了一种新的反应模式.
- 这些发现扩大了C-H激活化学的范围,包括了活性化物元素.
相关概念视频
Acid Halides to Ketones: Gilman Reagent
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen double...
Preparation of Nitriles
One of the common methods to prepare nitriles is the dehydration of amides. This method requires strong dehydrating agents like phosphorous pentoxide or boiling acetic anhydride for converting amides to nitriles. Another reagent namely, thionyl chloride also accomplishes the dehydration of amides, where amide acts as a nucleophile. The first step of the mechanism involves the nucleophilic attack by the amide on the thionyl chloride to form an intermediate. In the next step, the electron pairs...
Nitriles to Carboxylic Acids: Hydrolysis
Nitriles undergo acid-catalyzed hydrolysis or base-catalyzed hydrolysis to form a carboxylic acid. These reactions proceed via an amide intermediate.
Nitriles to Ketones: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert nitriles to ketones and proceed through a nucleophilic acyl substitution. Nitriles react with a Grignard reagent, followed by an aqueous acid, to yield ketones. The reaction introduces a new carbon–carbon bond. The alkyl–magnesium bond in the Grignard reagent is highly polar, so the alkyl carbon develops a carbanionic character and acts as a nucleophile.
The mechanism begins with a nucleophilic attack by the Grignard reagent...
The mechanism begins with a nucleophilic attack by the Grignard reagent...
Diazonium Group Substitution: –OH and –H
Nitrous acid, a weak acid, is prepared in situ via the reaction of sodium nitrite with a strong acid under cold conditions. This nitrous acid prepared in situ reacts with primary arylamines to form arenediazonium salts. Such reactions are known as diazotization reactions. As shown in Figure 1, the formation of arenediazonium salts begins with the decomposition of nitrous acid in an acidic solution to give nitrosonium ions.
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Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...


