Structure correlations among arylpyran pseudoacids and derivatives

IF 2.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Structural Chemistry Pub Date : 2024-09-03 DOI:10.1007/s11224-024-02364-8
Michael Nguyen, Marilyn Brooks, Emily O’Loughlin, Edward J. Valente
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Abstract

Many 4- and 5-oxocarboxylic acids show open-cyclic solution racemization/tautomerism including the dehydration-resistant arylpyran pseudoacid 3-hydroxy-4,4-dimethylisobenzopyran-1-one. The crystal and molecular structures of nine α-anomeric derivatives (including 11 distinct molecular structures) of this pseudoacid (or close analogs) have been determined, including pseudoacyl chlorides, normal, pseudoanhydrides, a dipseudoanhydride, and a tertiary pseudoamide. The basicity of the implied exocyclic leaving groups span 40 pK units. Together with seven closely related pseudoacid molecular structures previously determined, a data set containing 18 compounds was generated. Exocyclic C–O bonds shortened as endocyclic C–O bonds lengthened in linear functions of exocyclic leaving group basicity with l(xC-O, Å) = 1.4426 − 0.00400 * pKa, N = 13, R2 = 0.969; l(nC-O, Å) = 1.4204 + 0.00205 * pKa, N = 18, R2 = 0.951. These correlations were compared with results for other α-anomeric pyranoid systems, tetrahydropyran and dihydropyran, and an arylfuran pseudoacyl system. Exocyclic substituents effectively modified endocyclic C–O bond polarities over a considerable range.

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芳基吡喃假酸及其衍生物的结构相关性
许多 4-和 5-氧代羧酸显示出开环溶液外消旋化/同分异构现象,其中包括抗脱水芳基吡喃假酸 3-羟基-4,4-二甲基异苯并呋喃-1-酮。已测定了这种假酸(或近似物)的九种 α-异构体衍生物(包括 11 种不同的分子结构)的晶体和分子结构,其中包括假酰基氯化物、正常的假酸酐、一种二假酸酐和一种三级假酰胺。隐含的外环离去基团的碱性跨越了 40 个 pK 单位。加上之前确定的七个密切相关的假酸类分子结构,生成了一个包含 18 种化合物的数据集。在外环离去基团碱性的线性函数中,外环 C-O 键缩短,内环 C-O 键延长,l(xC-O, Å) = 1.4426 - 0.00400 * pKa,N = 13,R2 = 0.969;l(nC-O, Å) = 1.4204 + 0.00205 * pKa,N = 18,R2 = 0.951。这些相关性与其他 α-异构吡喃体系、四氢吡喃和二氢吡喃以及芳基呋喃假酰基体系的结果进行了比较。外环取代基在相当大的范围内有效地改变了内环 C-O 键的极性。
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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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