Synthesis, Spectroscopic Study and Crystal Structure of a New Single-Enantiomer C(O)NHP(O)-based Phosphoric Triamide, CCl&lt;sub&gt;3&lt;/sub&gt;C(O)NHP(O)[(R)-(+)-NHCH(CH&lt;sub&gt;3&lt;/sub&gt;)(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;5&lt;/sub&gt;)]&lt;sub&gt;2&lt;/sub&gt;·0.25H&lt;sub&gt;2&lt;/sub&gt;O

Ariani, Maral; Pourayoubi, Mehrdad; Dušek, Michal; Alviri, Banafsheh Vahdani; Eigner, Václav; Damodaran, Krishnan

doi:10.2116/xraystruct.33.17

Cited by 2 publications

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“…The P atoms display a distorted tetrahedral environment of (O) 2 P(O)(N) for (I) and (II), and (N) 2 P(O)(N) for (III). In general, all the bond lengths and angles are within the expected values observed in analogous structures and according to the atoms involved (Vahdani Alviri et al, 2020;Ariani et al, 2017). The P-O-C angles in (I) and (II), for example, the P1-O2-C1 angle in (I) of 124.99 (13) (Table 2), demonstrate the hybridization state of the ester O atoms as being near to sp 2 , similar to the hybridization reported for analogous compounds (Vahdani Alviri et al, 2018).…”

Section: X-ray Descriptionsupporting

confidence: 80%

“…Chiral phosphoramides are well known for some biochemical properties, typically in the formulation of different classes of drugs (Warren et al, 2016), and offer a promising perspective toward developing diverse systems, such as enantioselective catalysts (Liao et al, 2019) and chiral adsorbent polymers (Ahmadabad et al, 2019). Some subclasses of phosphoramides, for example, amidophosphoesters and phosphoric triamides, were studied with respect to chirality and have attracted much attention for further studies (Sabbaghi et al, 2019;Ariani et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

“…The P O group in a phosphoramide shows a good hydrogen-bond acceptor capability (Eghbali Toularoud et al, 2018), which is a suitable property for applications related to sorption; thus, chiral phosphoramide-based polymers were manufactured and used for the separation of single enantiomers from their racemic mixtures (Ahmadabad et al, 2019). Recently, we have reported the first enantiomeric pair for both (O) 2 P(O)(N)-based (Sabbaghi et al, 2019) and C(O)NH-P(O)(N) 2 -based structures (Eghbali Toularoud et al, 2018), and some single-enantiomer compounds belonging to different families, including both small molecules and macromolecules (Ariani et al, 2017;Ahmadabad et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

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Structural differences/similarities of diastereotopic groups in three new chiral phosphoramides

et al. 2021

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The crystal structures of two single-enantiomer amidophosphoesters with an (O)2P(O)(N) skeleton and one single-enantiomer phosphoric triamide with an (N)2P(O)(N) skeleton were studied. The compounds are diphenyl [(R)-(+)-α-4-dimethylbenzylamido]phosphate, (I), and diphenyl [(S)-(−)-α-4-dimethylbenzylamido]phosphate, (II), both C21H22NO3P, and N-(2,6-difluorobenzoyl)-N′,N′′-bis[(R)-(+)-α-ethylbenzyl]phosphoric triamide, C25H28F2N3O2P, (III). The asymmetric units contain two amidophosphoester molecules for (I) and (II), and one phosphoric triamide molecule for (III). In the crystal structures of (I) and (II), molecules are assembled in a similar one-dimensional chiral ribbon architecture, but with almost a mirror-image relationship with respect to each other through N—H...O(P) and C—H...O(P) hydrogen bonds along [010]. In the crystal structure of (III), the chiral tape architecture along [100] is mediated by N—H...O(P) and N—H...O(C) hydrogen bonds, and the tapes are connected into slabs by C—H...O interactions (along the ab plane). The differences/similarities of the two diastereotopic phenoxy groups in (I)/(II) and the two chiral amine fragments in (III) were studied on the grounds of geometry, conformation and contribution to the crystal packing, as well as 1H and 13C signals in a solution NMR study.

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Section: X-ray Descriptionsupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural differences/similarities of diastereotopic groups in three new chiral phosphoramides

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“…The crystal structures of chiral phosphoric triamides are absent in the CSD; therefore, we were interested in the synthesis and X-ray crystal structure analysis of chiral phosphoric triamide molecules in order to study the influence of chirality on the hydrogen-bond pattern. In a previous article, we reported the X-ray crystal structure of the first chiral [RC(O)NH](R 1 R 2 N) 2 P(O) phosphoric triamide, namely [CCl 3 -C(O)NH][R-(+)(C 6 H 5 )CH(CH 3 )NH] 2 P(O)Á0.25H 2 O (Ariani et al, 2017); however, an attempt to analyse its enantiomer by X-ray diffraction was unsuccessful.…”

Section: Introductionmentioning

confidence: 99%

Chiral one-dimensional hydrogen-bonded architectures constructed from single-enantiomer phosphoric triamides

et al. 2018

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The two single-enantiomer phosphoric triamides N-(2,6-difluorobenzoyl)-N',N''-bis[(S)-(-)-α-methylbenzyl]phosphoric triamide, [2,6-F-CHC(O)NH][(S)-(-)-(CH)CH(CH)NH]P(O), denoted L-1, and N-(2,6-difluorobenzoyl)-N',N''-bis[(R)-(+)-α-methylbenzyl]phosphoric triamide, [2,6-F-CHC(O)NH][(R)-(+)-(CH)CH(CH)NH]P(O), denoted D-1, both CHFNOP, have been investigated. In their structures, chiral one-dimensional hydrogen-bonded architectures are formed along [100], mediated by relatively strong N-H...O(P) and N-H...O(C) hydrogen bonds. Both assemblies include the noncentrosymmetric graph-set motifs R(10), R(6) and C(8), and the compounds crystallize in the chiral space group P1. Due to the data collection of L-1 at 120 K and of D-1 at 95 K, the unit-cell dimensions and volume show a slight difference; the contraction in the volume of D-1 with respect to that in L-1 is about 0.3%. The asymmetric units of both structures consist of two independent phosphoric triamide molecules, with the main difference being seen in one of the torsion angles in the OPNHCH(CH)(CH) part. The Hirshfeld surface maps of these levo and dextro isomers are very similar; however, they are near mirror images of each other. For both structures, the full fingerprint plot of each symmetry-independent molecule shows an almost asymmetric shape as a result of its different environment in the crystal packing. It is notable that NMR spectroscopy could distinguish between compounds L-1 and D-1 that have different relative stereocentres; however, the differences in chemical shifts between them were found to be about 0.02 to 0.001 ppm under calibrated temperature conditions. In each molecule, the two chiral parts are also different in NMR media, in which chemical shifts and P-H and P-C couplings have been studied.

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Synthesis, Spectroscopic Study and Crystal Structure of a New Single-Enantiomer C(O)NHP(O)-based Phosphoric Triamide, CCl<sub>3</sub>C(O)NHP(O)[(R)-(+)-NHCH(CH<sub>3</sub>)(C<sub>6</sub>H<sub>5</sub>)]<sub>2</sub>·0.25H<sub>2</sub>O

Cited by 2 publications

References 9 publications

Structural differences/similarities of diastereotopic groups in three new chiral phosphoramides

Structural differences/similarities of diastereotopic groups in three new chiral phosphoramides

Chiral one-dimensional hydrogen-bonded architectures constructed from single-enantiomer phosphoric triamides

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