Diastereoselective Synthesis of α-Quaternary Aziridine-2-carboxylates via Aza-Corey–Chaykovsky Aziridination of <i>N</i>-<i>tert</i>-Butanesulfinyl Ketimino Esters

Marsini, Maurice A.; Reeves, Jonathan T.; Desrosiers, Jean‐Nicolas; Herbage, Melissa A.; Savoie, Jolaine; Li, Zhibin; Fandrick, Keith R.; Sader, C. Avery; McKibben, Bryan P.; Gao, Donghong A.; Cui, Jianwen; Gonnella, Nina C.; Lee, Heewon; Wei, Xudong; Roschangar, Frank; Lu, Biao; Senanayake, Chris H.

doi:10.1021/acs.orglett.5b02838

Cited by 64 publications

(26 citation statements)

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“…In Tables , we listed all published α‐amino acid derivatives and (either linear or, more rarely, cyclic) peptides to the decamer level where single or consecutive fully‐extended (C 5 ) structures were identified by X‐ray diffraction in the last 5/6 years. A few, still unpublished 3D‐structures, characterized by the C 5 form and solved in the Padova laboratory, are presented in Table…”

Section: Detailed Literature Survey On Peptides Since 2012mentioning

confidence: 99%

The fully‐extended conformation in peptides and proteins

et al. 2018

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The intramolecularly H‐bonded, fully‐extended conformation (C5) of an α‐amino acid residue (and the resulting 2.05‐helix obtained via its propagation) is one of the least extensively investigated types of peptide and protein backbone secondary structure. This situation does still currently occur despite its unique ability to enjoy by far the largest separation per residue among peptide conformations. In this article, we offer a detailed update of our present knowledge on this intriguing 3D‐structure of peptides in the crystal state as obtained from recently published investigations, complemented by a statistical analysis for its occurrence in the crystal structures of α‐amino acid derivatives and peptides available in the Cambridge Structural Database. We have expanded this useful information to the results of a bioinformatics analysis performed on this (so far largely unappreciated) conformation authenticated in all proteins solved by X‐ray diffraction to a resolution of ≤ 1.5 Å. In the last section, we describe the results of our DFT calculations on the conformational preferences of a set of homopeptides (from monomer to octamer) based on as many as six proteins and two noncoded, carefully selected, α‐amino acids. From this literature survey integrated by new energy calculations, we have definitely provided strong support to the thesis that this polypeptide 3D‐structure does indeed exist, it should be not neglected in future studies by structural biochemists, and it represents a very attractive, novel backbone for applications for organic, medicinal, and biomaterials chemists.

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Section: Detailed Literature Survey On Peptides Since 2012mentioning

confidence: 99%

The fully‐extended conformation in peptides and proteins

et al. 2018

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“…Under similar conditions, Corey–Chaykovsky aziridination of ketimino ester 51 gave rise to α‐trifluoromethyl α‐amino acid derivative 52 (Scheme ) . The reaction proceeded with excellent diastereoselectivity, but with rather low yield, probably due to the very high reactivity of extremely electrophilic ketimine 51…”

Section: Reactivity Of (Ss)‐n‐tert‐butylsulfinyl‐333‐trifluoroacmentioning

confidence: 90%

“…It should be noted that the observed ( S s )( S )‐absolute configuration of 52 is stereochemically equivalent to that of aziridines ( S s )( R )‐ 50 (Scheme ), underscoring the stereodirecting properties of a trifluoromethyl group.…”

Section: Reactivity Of (Ss)‐n‐tert‐butylsulfinyl‐333‐trifluoroacmentioning

confidence: 90%

N‐tert‐Butylsulfinyl‐3,3,3‐trifluoroacetaldimine: Versatile Reagent for Asymmetric Synthesis of Trifluoromethyl‐Containing Amines and Amino Acids of Pharmaceutical Importance

et al. 2016

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Synthetic methods for the preparation of compounds containing trifluoromethyl groups are in extremely high demand in nearly every sector of the chemical industry. Over the last several years the chemistry of N‐tert‐butylsulfinyl‐3,3,3‐trifluoroacetaldimine has undergone particular development. Currently, it is commonly used as a versatile reagent for general asymmetric synthesis of trifluoromethyl‐containing amines and amino acids of pharmaceutical potential. This review provides a critical and comprehensive overview of synthetic applications of this reagent as well as of several relevant analogues, such as aldimines containing –CHF2, –CClF2, –CBrF2, and –CF2P(O)(OEt)2 groups and N‐tert‐butylsulfinyl‐3,3,3‐trifluoromethyl‐substituted ketimines. Where it is possible, we emphasize the structural novelty and pharmaceutic value of the products obtainable by application of these reagents.

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“…To the best of our knowledge, there is only one example in which (S)-N-tertbutylsulfinyl imine of ethyl trifluoropyruvate was used for the diastereoselective synthesis of α-trifluoromethylated aziridine-2-carboxylate via aza-Corey-Chaykovsky reaction. [5] In the present work, we describe the convenient synthesis and some diastereoselective transformations of enantiomeric (S)-and (R)-N-tert-butylsulfinyl imines of methyl trifluoropyruvate.…”

Section: Introductionmentioning

confidence: 99%