关于胺基介导的电友性烯玻利化及其在MIDA酸盐合成中的应用的机制研究
Viktor Bagutski1, Alessandro Del Grosso, Josue Ayuso Carrillo
1Department of Chemistry, University of Manchester, Manchester, M13 9PL, United Kingdom.
Journal of the American Chemical Society
|December 5, 2012
概括
通过使用Y(2)BCl和AlCl(3) 与胺基实现了对和异的直接电友性化. 这种方法产生稳定的MIDA-酸盐,并通过S(E) Ar机制与酸为活性基质进行处理.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
- 合成方法论 合成方法论
背景情况:
- 电友性玻里化是合成有机化合物的关键转化.
- 开发有效和多用途的直接化方法仍然是一个活跃的研究领域.
研究的目的:
- 为广泛的和异开发一种直接电友性化方法.
- 调查反应机制并确定关键中间体.
- 为了能够合成稳定的MIDA-酸.
主要方法:
- 使用Y(2)BCl (Y(2) = Cl(2) 或o-catecholato) 与等等分子AlCl(3) 和三级氨基的直接电友性化.
- 在现场功能化ArBCl(2) 产品与TMS(2) MIDA.
- 结合实验和计算研究来阐明反应机制.
主要成果:
- 在中等到良好的产量中,成功化各种和异.
- 形成稳定的MIDA-博酸盐.
- 鉴定酸,[Y(2) B(胺) ](+),作为激活的S(E) Ar机制中的关键电友.
- 两种氨基依赖性途径的化,用于catecholato-borocations.
- 鉴定了弱活化的替代机制,以及与大型氨基的反应.
结论:
- 已经建立了一个通用的直接电友性玻利化协议.
- 这项研究提供了对各种芳香基质的化过程的机制性见解.
- 开发的方法提供了一条实用的途径,以获得有价值的MIDA-酸构建块.
相关概念视频
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Preparation of Amines: Reductive Amination of Aldehydes and Ketones
Carbonyl compounds and primary amines undergo reductive amination first to produce imines, followed by secondary amines in the same reaction mixture, using selective reducing agents like sodium cyanoborohydride or sodium triacetoxyborohydride. Reductive amination produces different degrees of substitution of amines depending on the starting amine substrate.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Amines to Amides: Acylation of Amines
Various carboxylic acid derivatives (such as acid chlorides, esters, and anhydrides) can be used for the acylation of amines to yield amides. The reaction requires two equivalents of amines. The first amine molecule functions as a nucleophile and attacks the carbonyl carbon to produce a tetrahedral intermediate. This is followed by the loss of the leaving group and restoration of the C=O bond.
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
Next, the second equivalent of amine serves as a Brønsted base and deprotonates the quaternary amide...
Electrophilic Aromatic Substitution: Nitration of Benzene
The nitration of benzene is an example of an electrophilic aromatic substitution reaction. It involves the formation of a very powerful electrophile, the nitronium ion, which is linear in shape. The reaction occurs through the interaction of two strong acids, sulfuric and nitric acid.


