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Thiourea Derivative of 2-[(1R)-1-Aminoethyl]phenol: A Flexible Pocket-like Chiral Solvating Agent (CSA) for the Enantiodifferentiation of Amino Acid Derivatives by NMR Spectroscopy
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-03-19 , DOI: 10.1021/acs.joc.0c00027
Alessandra Recchimurzo 1 , Cosimo Micheletti 1 , Gloria Uccello-Barretta 1 , Federica Balzano 1
Affiliation  

Thiourea derivatives of 2-[(1R)-1-aminoethyl]phenol, (1S,2R)-1-amino-2,3-dihydro-1H-inden-2-ol, (1R,2R)-(1S,2R)-1-amino-2,3-dihydro-1H-inden-2-ol, and (R)-1-phenylethanamine have been compared as chiral solvating agents (CSAs) for the enantiodiscrimination of derivatized amino acids using nuclear magnetic resonance (NMR) spectroscopy. Thiourea derivative, prepared by reacting 2-[(1R)-1-aminoethyl]phenol with benzoyl isothiocyanate, constitutes an effective CSA for the enantiodiscrimination of N-3,5-dinitrobenzoyl (DNB) derivatives of amino acids with free or derivatized carboxyl functions. A base additive 1,4-diazabicyclo[2.2.2]octane(DABCO)/N,N-dimethylpyridin-4-amine (DMAP)/NBu4OH) is required both to solubilize amino acid derivatives with free carboxyl groups in CDCl3 and to mediate their interaction with the chiral auxiliary to attain efficient differentiation of the NMR signals of enantiomeric substrates. For ternary systems CSA/substrate/DABCO, the chiral discrimination mechanism has been ascertained through the NMR determination of complexation stoichiometry, association constants, and stereochemical features of the diastereomeric solvates.

中文翻译:


2-[(1R)-1-氨基乙基]苯酚的硫脲衍生物:一种灵活的袋状手性溶剂 (CSA),用于通过 NMR 光谱对氨基酸衍生物进行对映分化



2-[( 1R )-1-氨基乙基]苯酚的硫脲衍生物,( 1S , 2R )-1-氨基-2,3-二氢-1H-茚-2-醇,( 1R , 2R )-(1 S ,2 R )-1-氨基-2,3-二氢-1 H -茚-2-醇和 ( R )-1-苯乙胺作为手性溶剂化剂 (CSA) 进行了对映体歧视的比较使用核磁共振(NMR)光谱分析衍生化氨基酸。硫脲衍生物是通过 2-[(1 R )-1-氨基乙基]苯酚与异硫氰酸苯甲酰酯反应制备的,可构成有效的 CSA,用于对具有游离或衍生羧基的氨基酸的N- 3,5-二硝基苯甲酰基 (DNB) 衍生物进行对映区分功能。需要碱添加剂 1,4-二氮杂双环[2.2.2]辛烷 (DABCO)/ N , N-二甲基吡啶-4-胺 (DMAP)/NBu 4 OH) 才能将具有游离羧基的氨基酸衍生物溶解在 CDCl 3中并介导它们与手性助剂的相互作用,以实现对映体底物的 NMR 信号的有效区分。对于三元体系 CSA/底物/DABCO,通过 NMR 测定非对映体溶剂化物的络合化学计量、缔合常数和立体化学特征,确定了手性辨别机制。
更新日期:2020-04-24
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