Dataset Information

Attached Nitrogen Test by ¹³C-¹⁴N Solid-State NMR Spectroscopy for the Structure Determination of Heterocyclic Isomers.

ABSTRACT: Differentiation of heterocyclic isomers by solution ¹H, ¹³C, and ¹⁵N NMR spectroscopy is often challenging due to similarities in their spectroscopic signatures. Here, ¹³C{¹⁴N} solid-state NMR spectroscopy experiments are shown to operate as an "attached nitrogen test", where heterocyclic isomers are easy to distinguish based on one-dimensional nitrogen-filtered ¹³C solid-state NMR. We anticipate that these NMR experiments will facilitate the assignment of heterocyclic isomers during synthesis and natural product discovery.

SUBMITTER: Dorn RW

PROVIDER: S-EPMC9933616 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

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Attached Nitrogen Test by 13C-14N Solid-State NMR Spectroscopy for the Structure Determination of Heterocyclic Isomers.

Dorn Rick W RW Wall Brendan J BJ Ference Sarah B SB Norris Sean R SR Lubach Joseph W JW Rossini Aaron J AJ VanVeller Brett B

Organic letters 20220622 31

Differentiation of heterocyclic isomers by solution 1H, 13C, and 15N NMR spectroscopy is often challenging due to similarities in their spectroscopic signatures. Here, 13C{14N} solid-state NMR spectroscopy experiments are shown to operate as an "attached nitrogen test", where heterocyclic isomers are easy to distinguish based on one-dimensional nitrogen-filtered 13C solid-state NMR. We anticipate that these NMR experiments will fa ...[more]

PMID: 35731042

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Project description:Accurate distance measurements between proton and nitrogen can provide detailed information on the structures and dynamics of various molecules. The combination of broadband phase-modulated (PM) pulse and rotational-echo saturation-pulse double-resonance (RESPDOR) sequence at fast magic-angle spinning (MAS) has enabled the measurement of multiple 1H-14N distances with high accuracy. However, complications may arise when applying this sequence to systems with multiple inequivalent 14N nuclei, especially a single 1H sitting close to multiple 14N atoms. Due to its broadband characteristics, the PM pulse saturates all 14N atoms; hence, the single 1H simultaneously experiences the RESPDOR effect from multiple 1H-14N couplings. Consequently, no reliable H-N distances are obtained. To overcome the problem, selective 14N saturation is desired, but it is difficult because 14N is an integer quadrupolar nucleus. Alternatively, 14N overtone (OT) NMR spectroscopy can be employed owing to its narrow bandwidth for selectivity. Moreover, owing to the sole presence of two energy levels (m = ± 1), the 14N OT spin dynamics behaves similarly to that of spin-1/2. This allows the interchangeability between RESPDOR and rotational-echo double-resonance (REDOR) since their principles are the same except the degree of 14N OT population transfer; saturation for the former whereas inversion for the latter. As the ideal saturation/inversion is impractical due to the slow and orientation-dependent effective nutation of 14N OT, the working condition is usually an intermediate between REDOR and RESPDOR. The degree of 14N OT population transfer can be determined from the results of protons with short distances to 14N and then can be used to obtain long-distance determination of other protons to the same 14N site. Herein, we combine the 14N OT and REDOR/RESPDOR to explore the feasibility of selective 1H-14N distance measurements. Experimental demonstrations on simple biological compounds of L-tyrosine.HCl, N-acetyl-L-alanine, and L-alanyl-L-alanine were performed at 14.1 T and MAS frequency of 62.5 kHz. The former two consist of a single 14N site, whereas the latter consists of two 14N sites. The experimental optimizations and reliable fittings by the universal curves are described. The extracted 1H-14N distances by OT-REDOR are in good agreement with those determined by PM-RESPDOR and diffraction techniques.

Dataset Information

Attached Nitrogen Test by ¹³C-¹⁴N Solid-State NMR Spectroscopy for the Structure Determination of Heterocyclic Isomers.

Publications

Attached Nitrogen Test by <sup>13</sup>C-<sup>14</sup>N Solid-State NMR Spectroscopy for the Structure Determination of Heterocyclic Isomers.

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