S3 HMBC: Spin-State-Selective HMBC for accurate measurement of homonuclear coupling constants. Application to strychnine yielding thirteen hitherto unreported JHH

• Published in: Journal of magnetic resonance (1997) Vol. 263; pp. 101 - 107
• Main Authors: Kjaerulff, Louise, Benie, Andrew J., Hoeck, Casper, Gotfredsen, Charlotte H., Sørensen, Ole W.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01-02-2016
• Subjects: HMBC; J coupling constants; RDC; S3 HMBC; Small molecules; RDC; Small molecules; J coupling constants; S3 HMBC; HMBC
• ISSN: 1090-7807; 1096-0856
• DOI: 10.1016/j.jmr.2015.11.007

[Display omitted]
•S3 HMBC is a novel way of measuring ​homonuclear coupling constants and their signs.•Application of S3 HMBC to strychnine led to thirteen hitherto unreported JHH.
A novel method, Spin-State-Selective (S3) HMBC, for accurate measurement of homonuclear coupling constants is introduced. As characteristic for S3 techniques, S3 HMBC yields independent subspectra corresponding to particular passive spin states and thus allows determination of coupling constants between detected spins and homonuclear coupling partners along with relative signs. In the presented S3 HMBC experiment, spin-state selection occurs via large one-bond coupling constants ensuring high editing accuracy and unequivocal sign determination of the homonuclear long-range relative to the associated one-bond coupling constant. The sensitivity of the new experiment is comparable to that of regular edited HMBC and the accuracy of the J/RDC measurement is as usual for E.COSY and S3-type experiments independent of the size of the homonuclear coupling constant of interest. The merits of the method are demonstrated by an application to strychnine where thirteen JHH coupling constants not previously reported could be measured.