基于新型有机小分子催化的不对称烯丙基化反应及Diels-Alder反应研究

In the light of the characteristics of small molecules organocatalysis and the theory of Lewis acid activation, the synthesized new organocatalysts will be used in the study of asymmetric allylation reaction and Diels-Alder reaction. (1) The "aminophenols" are designed and synthesized from natural amino acid and the substituted salicylaldehyde, while the "amino alcohols" are synthesized from unnatural β-hydroxyl-α-amino acids; Based on the strategy of relay catalysis, hydrogen bond activation and buffer solution promoted catalyst's regeneration, the activated boron Lewis acid catalyst derived from "aminophenol" and "amino alcohol" are formed and applied to catalyze the reaction of allylation reactions of pinacol allyl boron with activated imines and carbonyl compounds. The catalyst substituent, the activation group of the activated imines, the hydrogen bond formation and the ability of the catalyst regeneration will be considered in the selectivity and activity of the catalytic reaction. (2) The "aminophenols" and "amino alcohols" are used to react with arylboronic acid to get "1, 3-oxazine borane" and "oxazaborolidines", respectively. The Br?nsted or Lewis acid activated 1, 3-oxazine borane and oxazaborolidines were used to catalyze the asymmetric Diels-Alder reactions. The structure of borane structure and the the type of acid will be applied to discuss the activity and the selectivity of the catalytic reaction. Implementation of this project will help the development of new organic small molecular catalysts, put forward new types of organic small molecule catalysts in the catalytic pathway of allylation reaction and Diels-Alder reaction, improve and widen the application of organic small molecules in asymmetric catalytic reactions.

本项目根据有机小分子催化特点及Lewis酸活化理论，设计合成新型有机小分子催化剂并将其应用于不对称烯丙基化反应和Diels-Alder反应研究。（1）设计合成基于天然氨基酸和取代水杨醛的"氨基酚"有机小分子催化剂、基于非天然β-羟基-α-氨基酸的"氨基醇"有机小分子催化剂；通过"氨基酚"及"氨基醇"现场形成的活化硼Lewis酸催化烯丙基硼与活化亚胺、羰基化合物的不对称烯丙基化反应。（2）将所设计合成的"氨基酚"及"氨基醇"催化剂分别与芳基硼酸反应生成"1,3-噁嗪硼烷"及"噁唑硼烷"，二者经酸活化后应用于催化不对称Diels-Alder反应。该项目的实施将有助于发展新型有机小分子催化剂，提出该类型有机小分子催化剂在不对称烯丙基化反应和Diels-Alder反应中的催化途径，完善和拓展有机小分子在不对称催化反应中的应用。

合成了氨基酚和噁唑硼烷类化合物，并将其应用于羰基化合物的烯丙基化反应，双边氨基酚化合物在催化不对称烯丙基化反应中存在协同效应，获得了较单边催化剂更好产率和对映选择性的烯丙基加成产物。基于单分子双活化及双分子协同活化理念，发展了三氯硅烷与醛、酰腙的烯丙基化反应，吡唑酮、靛红酮亚胺与烯丙基醋酸酯的Mannich-烯丙基化反应，靛红酮亚胺与TMSCN的不对称氰化反应；建立了廉价过渡金属催化的酰胺α-芳基化反应；通过调控反应条件，以芳基三氮烯同时作为芳基源和偶氮源，实现了吲哚区域和化学选择性的C2-芳基化反应和C3-偶氮化反应；以β, γ-不饱和酰胺和偶氮甲酸酯为底物，实现了β, γ-不饱和酰胺的区域选择性α-胺化及γ-胺化。通过分析上述反应分子间相互作用，提出了可能的催化及活化反应机理。此外，制备了多种石墨烯基复合物，研究了其作为电极对氨基酸对映体识别性能。通过将GO与手性小分子复合，制备了石墨烯基复合电极不仅具有对映选择性，而且可以对手性分子进行定量检测，这为手性氨基酸识别提供了新思路。