CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 2: <i>Cis‐</i> and <i>trans‐</i>3‐hydroxy‐4‐aryl/alkyl‐β‐lactams. A case study

Chen, Yihui; Petrovic, Ana G.; Roje, Marin; Kayser, Margaret M.; Yang, Yan; Berova, Nina; Proni, Gloria

doi:10.1002/chir.20718

Cited by 24 publications

(27 citation statements)

References 26 publications

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“…In most situations, MC/OPLS-2005 is believed to be sufficient for determining the dominant structure of the host/guest complex without the need for further characterization (NMR, IR). When, however, the computational procedure reveals the occurrence of previously unsuspected or anomalous coordination modes, the assistance of other methodologies (i.e., by FT-IR experiments and/or suitable transformations of the carrier) 6,7,44 is desirable. Percentage of structures displaying the indicated hydrogen bond.…”

Section: Resultsmentioning

confidence: 99%

CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 1: MC/OPLS‐2005 computational approach for predicting preferred interporphyrin helicity

et al. 2009

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This article describes a computational study on dimeric zinc porphyrin tweezer complexes with primary/secondary amines and secondary alcohols that validates the use of Optimized Potential for Liquid Simulations (OPLS-2005) as the lead computational choice for assisting the tweezer methodology in the absolute configurational assignment of organic compounds. A supramolecular, microscale approach known as the tweezer method has been widely applied in the past decade for determining the absolute configuration of chiral substrates that are difficult to study by other readily available methods. The method relies on a host/guest complexation mechanism between a porphyrin tweezer moiety and a substrate, after its conversion into a bidentate conjugate. The formation of 1:1 complexes is a stereodifferentiating process: upon complexation, the originally achiral tweezer adopts a preferential interporphyrin helicity, dictated by the absolute configuration of the chiral substrate. By correctly predicting the sign of the interporphyrin helicity in the complex, OPLS-2005 provides a correlation between the observed circular dichroism (CD) signal and the absolute configuration of the substrate. It also offers a great degree of insight into the structural factors responsible for chiral recognition and the amplitude of exciton couplets. Moreover, the preferential binding sites between the Zn-tweezer and secondary amine conjugates were revealed by using the new computational approach.

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Section: Resultsmentioning

confidence: 99%

CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 1: MC/OPLS‐2005 computational approach for predicting preferred interporphyrin helicity

et al. 2009

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“…It was more recently established 6,7 that a preferred interporphyrin helicity of the complex can be predicted by molecular mechanics (MM) calculations using the Monte Carlo (MC) algorithm, so that the correlation of observed exciton CD with AC can be made on more reliable theoretical basis. Molecular modeling conformational investigations are now carried out with the support of the recently developed force field OPLS-2005.…”

Section: Introductionmentioning

confidence: 99%

Bulky melamine‐based Zn‐porphyrin tweezer as a CD probe of molecular chirality

et al. 2011

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The transfer of chirality from a guest molecule to an achiral host is the subject of significant interest especially when, upon chiral induction, the chiroptical response of the host/guest complex can effectively report the absolute configuration (AC) of the guest. For more than a decade, dimeric metalloporphyrin hosts (tweezers) have been successfully applied as chirality probes for determination of the AC for a wide variety of chiral synthetic compounds and natural products. The objective of this study is to investigate the utility of a new class of melamine-bridged Zn-porphyrin tweezers as sensitive AC reporters. A combined approach based on an experimental CD analysis and a theoretical prediction of the prevailing interporphyrin helicity demonstrates that these tweezers display favorable properties for chiral recognition. Herein, we discuss the application of the melamine-bridged tweezer to the chiral recognition of a diverse set of chiral guests, such as 1,2-diamines, α-amino-esters and amides, secondary alcohols, and 1,2-amino-alcohols. The bulky periphery and the presence of a rigid porphyrin linkage lead, in some cases, to a more enhanced CD sensitivity than that reported earlier with other tweezers.

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“…Chiroptical responses are a very valuable tool in structure elucidation. The high sensitivity of chiroptical responses to conformational changes and supramolecular interactions has been exploited not only for absolute configuration determination, but also for conformational assignment and characterization of complexes . This chiroptical‐response dependence on the conformation typically leads chiral systems featuring several conformations in solution to present low chiroptical intensities .…”

Section: Methodsmentioning

confidence: 99%

Diverse Chiral Scaffolds from Diethynylspiranes: All‐Carbon Double Helices and Flexible Shape‐Persistent Macrocycles

Castro‐Fernández

Ren

García

et al. 2017

Chemistry A European J

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State-of-the-art chiroptical spectroscopies are valuable tools for structural elucidation. However, the potential of these spectroscopies for everyday applications has not been exploited to date partially due to the lack of sufficiently stable and efficient chiroptical systems. To this end, the development of suitable chiroptical structures is essential. Herein, we present the synthesis of spiro-compounds (P )-1 and (P )-2 as well as (M )-1 and (M )-2 exhibiting remarkable chiroptical responses. Theoretical simulations show that (P )-1, constituted by two (P)-configured spiranic chiral axes, presents an all-carbon double helix structure with (M)-helicity. On the other hand, molecular dynamic simulations reveal (P )-2 to have a single path for geometry-modification along its flat conformational space, certifying it as a chiral flexible shape-persistent macrocycle. Geometric quantification of chirality has been used to compare the spiranic derivatives presented herein.

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CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 2: Cis‐ and trans‐3‐hydroxy‐4‐aryl/alkyl‐β‐lactams. A case study

Cited by 24 publications

References 26 publications

CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 1: MC/OPLS‐2005 computational approach for predicting preferred interporphyrin helicity

CD‐sensitive Zn‐porphyrin tweezer host‐guest complexes, part 1: MC/OPLS‐2005 computational approach for predicting preferred interporphyrin helicity

Bulky melamine‐based Zn‐porphyrin tweezer as a CD probe of molecular chirality

Diverse Chiral Scaffolds from Diethynylspiranes: All‐Carbon Double Helices and Flexible Shape‐Persistent Macrocycles

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