The Role of Fluorine in the Stereoselective Tandem Aza-Michael Addition to Acrylamide Acceptors: An Experimental and Theoretical Mechanistic Study

Santos Fustero; Gema Chiva; Julio Piera

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The Role of Fluorine in the Stereoselective Tandem Aza-Michael Addition to Acrylamide Acceptors: An Experimental and Theoretical Mechanistic Study

机译：氟在丙烯酰胺受体的立体选择性串联氮杂-迈克尔加成中的作用：实验和理论机制的研究

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Aza-Michael additions of alpha-amino esters to fluorinated acceptors take place in a highly stereoselective manner, to give partially modified PSI-[NHCH_2]retropeptides incorporating a hydrolytically stable trifluoroalanine mimic. The reaction mechanism has been investigated experimentally and theoretically, in order to explain theeffect of the trifluoromethyl group on the reactivity and the origins of the experimentally observed stereocontrol.The reaction is a two-step process, involving a tandem aza-Michael addition followed by a stereoselective hydrogen transfer. Both steps are base-catalyzed. The high level of stereocontrol is the result of a combination of electrostatic interactions and steric effects.

机译：α-氨基酯在氟化受体上的Aza-Michael加成反应以高度立体选择性的方式进行，从而得到结合了水解稳定的三氟丙氨酸模拟物的部分修饰的PSI- [NHCH_2]逆肽。为了解释三氟甲基对反应性的影响以及实验观察到的立体控制的起源，已经对该反应机理进行了实验和理论研究。反应是一个两步过程，涉及串联aza-Michael加成后加a立体选择性氢转移。这两个步骤都是碱催化的。高水平的立体声控制是静电相互作用和空间效应共同作用的结果。

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《Chemistry: A European journal》 |2007年第30期|共13页
作者
Santos Fustero; Gema Chiva; Julio Piera;
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正文语种 eng
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density functional calculations; diastereoselectivity; fluorine chemistry; Michael reaction; peptides;

机译：密度泛函计算;非对映选择性;氟化学;迈克尔反应;肽;

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1. The Role of Fluorine in the Stereoselective Tandem Aza-Michael Addition to Acrylamide Acceptors: An Experimental and Theoretical Mechanistic Study [J] . Santos Fustero, Gema Chiva, Julio Piera Chemistry: A European journal . 2007,第30期

机译：氟在丙烯酰胺受体的立体选择性串联氮杂-迈克尔加成中的作用：实验和理论机制的研究
2. Benzoquinone-induced stereoselective chloride migration in (eta(3)-allyl)palladium complexes. A theoretical mechanistic study complemented by experimental verification [J] . Szabo KJ. Organometallics . 1998,第9期

机译：苯醌诱导的（eta（3）-烯丙基）钯配合物中的立体选择性氯化物迁移。理论力学研究，辅以实验验证
3. Synthesis of Diverse Nitrogen Heterocycles via Palladium-Catalyzed Tandem Azide-Isocyanide Cross-Coupling/Cyclization: Mechanistic Insight using Experimental and Theoretical Studies [J] . Ansari Arshad J., Pathare Ramdas S., Maurya Antim K., Advanced synthesis & catalysis . 2018,第2期

机译：通过钯催化串联叠氮化物 - 异氰化物交叉耦合/环化合成各种氮杂环：使用实验和理论研究的机械洞察
4. Enantioselective access to pyrrolidine 3-carboxylates using tandem aza-Michael additions-radical cyclisations [C] . Frantisek Kafka, Ullrich Jahn European Symposium on Organic Chemistry . 2009

机译：使用串联AZA-MICHAEL添加 - 自由基环法对吡咯烷3-羧酸酯的映射性进入
5. Enantioselective conjugate additions to Meldrum's acid acceptors for the synthesis of quaternary centres and studies on persistent intramolecular carbon-hydrogen-X (X = oxygen, sulfur, bromium, chlorine, and fluorine) hydrogen bonds involving benzyl Meldrum's acids [D] . Wilsily, Ashraf 2009

机译：向Meldrum的酸受体进行对映选择性共轭加成，以合成季中心，并研究涉及苄基Meldrum酸的持久性分子内碳氢X（X =氧，硫，溴，氯和氟）氢键
6. 32-Hydroxypyridinone (32-HOPO) vinyl sulfonamide and acrylamide linkers: Aza-Michael addition reactions and the preparation of poly-HOPO chelators [O] . Gloria Martinez, Jayanthi Arumugam, Hollie K. Jacobs, -1

机译：32-羟基吡啶酮（32-跳高）乙烯基磺酰胺和丙烯酰胺接头：AZA-MICHAEL加法反应和聚集螯合剂的制备
7. A Regioselective and Stereoselective Synthesis of 2,5-Dichloro-2,5,9,9-tetramethyldecahydro-benzocycloheptene via Stepwise addition Reactions between α- himachalene and HCl: Experimental and Theoretical Study [O] . 2018

机译：通过α-喜马烯和HCl之间的逐步添加反应的2,5-二氯-2,5,9,9,9-四甲基二烷基苯庚烯的区域选择性和立体选择性合成：实验和理论研究
8. Synthetic and Mechanistic Studies in Fluorine Chemistry. New Developments in Organonitrogen Fluorine Chemistry. [R] . DesMarteau, D. D. 1983

机译：氟化学的合成与机理研究。有机氮氟化学的新进展。

The Role of Fluorine in the Stereoselective Tandem Aza-Michael Addition to Acrylamide Acceptors: An Experimental and Theoretical Mechanistic Study

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