title: Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C <--> (15)N HSQC-IMPEACH and (13)C <--> (15)N HMBC-IMPEACH correlation spectra.
abstract: Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method.
authors.affiliation: Rapid Structure Characterization Laboratory, Pharmaceutical Sciences, Schering-Plough Research Institute, Summit, NJ 07059, USA. gary.martin@spcorp.com
authors.forename: Gary E
authors.initials: GE
authors.lastname: Martin
authors.forename: Bruce D
authors.initials: BD
authors.lastname: Hilton
authors.forename: Patrick A
authors.initials: PA
authors.lastname: Irish
authors.forename: Kirill A
authors.initials: KA
authors.lastname: Blinov
authors.forename: Antony J
authors.initials: AJ
authors.lastname: Williams
mesh_terms: D002247:Carbon Isotopes; D009682:Magnetic Resonance Spectroscopy / Q000379:methods*; D015394:Molecular Structure; D009587:Nitrogen Isotopes; D012984:Software; D013237:Stereoisomerism
chemical_list: D002247:Carbon Isotopes; D009587:Nitrogen Isotopes