ABSTRACT
An efficient and facile general method for the synthesis of conduritol C analogs, taking advantage of an enantioselective biocatalysis process of monosubstituted benzenes, is described. The absolute stereochemical patterns of the target molecules (−)-conduritol C, (−)-bromo-conduritol C, and (−)-methyl-conduritol C were achieved by means of chemoenzymatic methods. The stereochemistry present at the homochiral cyclohexadiene-cis-1,2-diols derived from the arene biotransformation and the enantioselective ring opening of a non-isolated vinylepoxide derivative permitted the absolute configuration of the carbon bearing the hydroxyl groups at the target molecules to be established. All three conduritols and two intermediates were crystallized, and their structures were confirmed by X-ray diffraction. The three conduritols and intermediates were isostructural. The versatility of our methodology is noteworthy to expand the preparation of conduritol C analogs starting from toluene dioxygenase (TDO) monosubstituted arene substrates.
Subject(s)
Cyclohexanols/chemical synthesis , Cyclohexenes/chemical synthesis , Biocatalysis , Biotransformation , Crystallography, X-Ray , Cyclohexanols/chemistry , Cyclohexenes/chemistry , Models, Molecular , Molecular Structure , StereoisomerismABSTRACT
The mol-ecule of the title keto carbasugar, C7H10O4, is formed by a cyclo-hexene skeleton with an envelope conformation, substituted by carbonyl, methyl and hydroxyl groups. The crystal structure is controlled mainly by a combination of strong O-Hâ¯O and weak C-Hâ¯O hydrogen bonds, forming nearly perpendicular chains running parallel to the [110] and [-110] directions. This perpendicularity is caused by a tetra-gonal pseudosymmetry influenced by the similarity between the a and b axes, the value of 90.9770â (10)° of the ß angle and the action of a 21 screw axis, which transform each chain into its corresponding nearly orthogonal one.
ABSTRACT
The absolute configuration of the title compound, C10H16O4, determined as 3aS,4S,5R,7aR on the basis of the synthetic pathway, was confirmed by X-ray diffraction. The mol-ecule contains a five- and a six-membered ring that adopt twisted and envelope conformations, respectively. The dihedral angle between the mean planes of the rings is 76.80â (11)° as a result of their cis-fusion. In the crystal, mol-ecules are linked by two pairs of O-Hâ¯O hydrogen bonds, forming chains along [010]. These chains are further connected by weaker C-Hâ¯O inter-actions along [100], creating (001) sheets that inter-act only by weak van der Waals forces.
ABSTRACT
The diastereoisomers of α-aminophosphonates are key intermediates in the synthesis of enantiomerically pure α-aminophosphonic acids, which are analogs of α-amino acids. Although several methods have been reported for the diastereoselective synthesis of α-aminophosphonates, their mass spectrometry (MS) fragmentation patterns have not yet been fully investigated. The work described here involved a detailed study of the fragmentation of enriched α-aminophosphonate diastereoisomers by chemical ionization (CI-MS) and fast atom bombardment (FAB)-MS. The complete characterization of the different conventional MS fragmentation pathways is represented and this intriguing exercise required the use of tandem mass spectrometry (MS/MS) experiments and high-resolution accurate mass measurements. All α-aminophosphonates gave prominent pseudomolecular ions, protonated molecules [MH](+) , and their fragmentations mainly showed a loss of dimethyl phosphite to give the corresponding iminium ions as base peaks for α-aminophosphonates bearing methylbenzyl and 2,2-dimethylbutyl fragments. The loss of the chiral fragment from the iminium ions bearing the (S)-1-(1-naphthyl)ethyl group gave rise to a base peak due to aryl cations. The nature of all fragment ions were confirmed by high-resolution mass spectrometry (HRMS).
