亚对称的形式 [3 + 3] - 循环添加反应中,子与电友性维尼尔碳中间体发生反应
Xiaochen Wang1, Xinfang Xu, Peter Y Zavalij
1Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.
Journal of the American Chemical Society
|September 22, 2011
概括
迪罗 (II) 碳酸盐催化剂有效地从和乙烯基酸乙酸盐中合成3,6-二-1,2-氧. 化催化剂在这些 [3+3] - 循环添加反应中提供高的反抗控制,使得不对称的合成成为可能.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 金属碳是有机合成中的多功能中间体.
- 循环添加反应是构建循环分子的基础.
- 在有机合成中,子是有价值的1,3-二极体.
研究的目的:
- 开发一种用于合成3,6-二-1,2-氧的催化方法.
- 为了在循环添加反应中获得高产量和酶选择性.
- 为了探索与各种子反应的范围.
主要方法:
- 迪罗 (II) 碳酸盐催化了和β-TBSO替代维尼尔酸之间的反应.
- 在非对称催化中使用性N-phthaloyl-(S) -氨基酸结合的二碳酸盐.
- 研究 [3+3]-循环添加反应与非循环和循环子.
主要成果:
- 获得了高产量的3,6-二-1,2-氧.
- 通过使用性二催化剂,可以实现出色的反控制.
- 该方法证明对非循环和循环子有效.
结论:
- 开发的二 ((II) 催化反应提供了一个有效的通道到3,6-dihydro-1,2-oxazines.
- 的催化剂使得这些异环化合物的高度酶选择性合成成为可能.
- 这种方法代表了不对称循环加法化学的重大进步.
相关概念视频
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Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
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The nitrosation reaction is one of the methods of preparing 1,2-diketones. The enol tautomer of the starting ketone reacts with sodium nitrite in hydrochloric acid, generating the 1,2-diketone after hydrolysis.
Conjugate Addition of Enolates: Michael Addition
The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.
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...
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