BINOL-3,3′-trifloneN,N-dimethyl phosphoramidites: Through-space 19F,31P spin-spin coupling with a remarkable dependency on temperature and solvent internal pressure

Kruck, Matthias, Munoz-Herranz, Maria ORCID: https://orcid.org/0000-0001-9037-349X, Bishop, Hannah L., Frost, Christopher G., Chapman, Christopher J., Kociok-Köhn, Gabriele, Butts, Craig P. and Lloyd-Jones, Guy C. (2008) BINOL-3,3′-trifloneN,N-dimethyl phosphoramidites: Through-space 19F,31P spin-spin coupling with a remarkable dependency on temperature and solvent internal pressure. Chemistry - A European Journal, 14 (26). pp. 7808-7812. ISSN 0947-6539

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Abstract

A combined computational and experimental study of the effects of solvent, temperature and stereochemistry on the magnitude of the through-space spin–spin coupling between 31P and 19F nuclei which are six-bonds apart is described. The reaction of 3-trifluoromethylsulfonyl-2,'2-dihydroxy-1,1'-binaphthalene (3-SO2CF3-BINOL) with hexamethylphosphorous triamide (P(NMe2)3) generates a pair of N,N-dimethylphosphoramidites which are diastereomeric due to their differing relative configurations at the stereogenic phosphorous centre and the axially chiral (atropisomeric) BINOL unit. Through-space NMR coupling of the 31P and 19F nuclei of the phosphoramidite and sulfone is detected in one diastereomer only. In the analogous N,N-dimethylphosphoramidite generated from 3,3'-(SO2CF3)2-BINOL only one of the diastereotopic trifluoromethylsulfone moieties couples with the 31P of the phosphoramidite. In both cases, the magnitude of the coupling is strongly modulated (up to 400?%) by solvent and temperature. A detailed DFT analysis of the response of the coupling to the orientation of the CF3 moiety with respect to the P-lone pair facilitates a confident assignment of the stereochemical identity of the pair of diastereomers. The analysis shows that the intriguing effects of environment on the magnitude of the coupling can be rationalised by a complex interplay of solvent internal pressure, molecular volume and thermal access to a wider conformational space. These phenomena suggest the possibility for the design of sensitive molecular probes for local environment that can be addressed via through-space NMR coupling.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry
UEA Research Groups:	Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017) Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Depositing User:	Rachel Smith
Date Deposited:	14 Feb 2012 16:39
Last Modified:	12 Jan 2023 15:30
URI:	https://ueaeprints.uea.ac.uk/id/eprint/37106
DOI:	10.1002/chem.200800825

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