Bare-minimum fluorous mixture synthesis of a stereoisomer library of 4,8,12-trimethylnonadecanols and predictions of NMR spectra of saturated oligoisoprenoid stereoisomers.

  title={Bare-minimum fluorous mixture synthesis of a stereoisomer library of 4,8,12-trimethylnonadecanols and predictions of NMR spectra of saturated oligoisoprenoid stereoisomers.},
  author={Edmund A.-H. Yeh and Eveline Kumli and Krishnan Damodaran and Dennis P. Curran},
  journal={Journal of the American Chemical Society},
  volume={135 4},
All four diastereomers of a typical saturated oligoisoprenoid, 4,8,12-trimethylnonadecanol, are made by an iterative three-step cycle with the aid of traceless thionocarbonate fluorous tags to encode configurations. The tags have a minimum number of total fluorine atoms, starting at zero and increasing in increments of one. With suitable acquisition and data processing, each diastereomer exhibits characteristic chemical shifts of methyl resonances in its (1)H and (13)C NMR spectra. Together… 
11 Citations

Figures and Tables from this paper

Synthesis and analysis of the all-(S) side chain of phosphomycoketides: a test of NMR predictions for saturated oligoisoprenoid stereoisomers.

The results suggest that a late-stage epimerization, not a failure of an asymmetric synthesis step, caused the formation of minor stereoisomers in the sample of pentamethylheptacosan-1-ol.

Development of Novel Fluorous Tagging Reagents and Progress Towards (4S,8S,12S)-4,8,12-Trimethylnonadecanol

Four new fluorous tagging reagents were synthesized and demonstrated to separate otherwise identical compounds and a simple method was developed to evaluate the potential of future fluorous tags.

(4S,6R)-4-methyl-6-pentyltetrahydro-2H-pyran-2-one as an efficient intermediate in the preparation of chiral building blocks with methyl-branched carbon skeleton. Application to the synthesis of bioactive compounds

Synthesis was performed of (3S)-3-methyldecen-1-ol and (4S)-4-methylundecen-1-ol, chiral alcohols with a methyl-branched carbon skeleton. The possibility of their application in asymmetric syntheses

Mechanistic and preparative studies of radical chain homolytic substitution reactions of N-heterocyclic carbene boranes and disulfides.

Reactions of 1,3-dimethylimidazol-2-ylidene-borane (diMe-Imd-BH3) and related NHC-boranes with diaryl and diheteroaryl disulfides provide diverse NHC-boryl monosulfides (diMe-Imd-BH2SAr) and

Influence of Electronic Effects on the Reactivity of Triazolylidene-Boryl Radicals: Consequences for the use of N-Heterocyclic Carbene Boranes in Organic and Polymer Synthesis.

A small library of triazolylidene-boranes that differ only in the nature of the aryl group on the external nitrogen atom was prepared and allowed a structure-reactivity relationship with regard to the substitution pattern of the NHC to be established and the role of electronic effects in the reactivity of NHC-boryl radicals to be probed.

Accessing Centnerszwer's quasiracemate – molecular shape controlled molecular recognition

M. Centnerszwer's seminal 1899 report investigated the stereochemical relationship between optical antipodes of different substances using melting-point behavior. One intriguing melting-point phase

Perfluorocarbons in Chemical Biology

How the unique properties of perfluorocarbons have been employed to understand and manipulate biological systems is described.



Minimal fluorous tagging strategy that enables the synthesis of the complete stereoisomer library of SCH725674 macrolactones.

Comparisons of spectra of 32 lactones and 16 ester precursors provide insights into when and why related compounds have the same or different spectra.

Total synthesis of a 28-member stereoisomer library of murisolins.

Total syntheses of two 16-member libraries of murisolin isomers are reported, with 12 isomerically pure murisolins new, while four match samples from the first library are reported.

Confirmation of the stereostructure of (+)-cytostatin by fluorous mixture synthesis of four candidate stereoisomers.

By a process of elimination (disproof), the isomer corresponding to cytostatin was determined, and the 4S,5S,6S,9S,10S,11S configuration confirmed.

Structure assignment of lagunapyrone B by fluorous mixture synthesis of four candidate stereoisomers.

Techniques of fluorous mixture synthesis have been used to make four candidate stereoisomers for the natural product lagunapyrone B, which was assigned the 6R,7S,19S,20S,21R configuration by comparison of optical rotations.

Stereoisomer libraries: total synthesis of all 16 stereoisomers of the pine sawfly sex pheromone by a fluorous mixture-synthesis approach.

Spectral data obtained for all 32 compounds matched well with published data, thereby validating the fluorous-tag encoding of diastereoisomers in the synthesis of multiple stereoisomers for spectroscopic studies, biological tests, or other structure-function relationships.

Total synthesis of enantiopure beta-D-mannosyl phosphomycoketides from Mycobacterium tuberculosis.

Biological evalutation of the all-S compound revealed that its antigenic potency for T cells is identical to that of the natural product, implying that the fine structure of the lipid part has a strong influence on biological activity and that the T cell response is discriminating between different stereoisomers.

Confirmation of the connectivity of 4,8,12,16,20-pentamethylpentacosylphoshoryl beta-D-mannopyranoside, an unusual beta-mannosyl phosphoisoprenoid from Mycobacterium avium, through synthesis.

Comparison of the electrospray and high-energy collision-induced dissociation mass spectra of the synthetic material with those reported for the isolate confirm the structure of this unusual antigenic substance with its modified isoprenoid chain.

A new method for the deoxygenation of secondary alcohols

On reaction with tributylstannane, O-cycloalkyl thiobenzoates and O-cycloalkyl S-methyl dithiocarbonates, derived from secondary alcohols, give good yields of the corresponding hydrocarbons. The

On the proof and disproof of natural product stereostructures: characterization and analysis of a twenty-eight member stereoisomer library of murisolins and their Mosher ester derivatives.

Characterizing a stereoisomer library of 28 of the 64 possible isomers of the acetogenin murisolin, including 24 of the 32 possible diastereomers, provides a complete picture of the spectra of this

A "shortcut" Mosher ester method to assign configurations of stereocenters in nearly symmetric environments. Fluorous mixture synthesis and structure assignment of petrocortyne A.

A "shortcut" of the advanced Mosher rule for use in assigning stereocenters in molecules with elements of local symmetry is proposed, and the chemical shifts of pairs of resonances related by local symmetry are subtracted from each other to provide the configuration.