An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines

Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described.     

Remote Regiocontrol by a Thioether Group in Diels-Alder Reactions of Naphthazarin: Regioselective Access to Tetracyclic Polyhydroxyquinones

The synthesis of tetracyclic polyhydroxyquinones 5a and 5b was achieved through a sequence involving two Diels-Alder reactions with 1-methoxy-1,3-cyclohexadiene: the first with 2-(p-tolylthio)naphthazarin and the second on the resulting tricyclic derivative previously transformed into a (p-tolylsulfinyl)naphthazarin. The success of this strategy stemmed from the efficient remote regiocontrol exerted by the thioether substituent in the first step.     

On the cube problem of Las Vergnas

We prove a conjecture of Las Vergnas in dimensions d7: The matroid of the d-dimensional cube C ^d has a unique reorientation class. This extends a result of Las Vergnas, Roudneff and Salaün in dimension 4. Moreover, we determine the automorphism group G ^d of the matroid of the d-cube C ^d for arbitrary dimension d, and we discuss its relation to the Coxeter group of C ^d . We introduce matroid facets of the matroid of the d-cube in order to evaluate the order of G ^d . These matroid facets turn out to be arbitrary pairs of parallel subfacets of the cube. We show that the Euclidean automorphism group W ^d is a proper subgroup of the group G ^d of all matroid symmetries of the d-cube by describing genuine matroid symmetries for each Euclidean facet. A main theorem asserts that any one of these matroid symmetries together with the Euclidean Coxeter symmetries generate the full automorphism group G ^d . For the proof of Las Vergnas' conjecture we use essentially these symmetry results together with the fact that the reorientation class of an oriented matroid is determined by the labeled lower rank contractions of the oriented matroid. We also describe the Folkman-Lawrence representation of the vertex figure of the d-cube and a contraction of it. Finally, we apply our method of proof to show a result of Las Vergnas, Roudneff, and Salaün that the matroid of the 24-cell has a unique reorientation class, too.