The First Synthesis of a Ribo-Hexos-5-Ulose: the L-Enantiomer

ABSTRACT

The title compound, previously unreported in either enantioform, and its 2,6-di-O-benzyl derivative have been synthesized through a stereocontrolled epimerization at C-2 of 6-O-protected methyl 3,4-O-isopropylidene-5-C-methoxy-β-D-galactopyranosides. The epimerization, performed through a high yielding sequence of oxidation-reduction owing to the cooperative role of the equatorial C-1 aglycon and the steric hindrance of the isopropylidene group, turned out to be completely diastereoselective. Whereas the unprotected L-ribo-hexos-5-ulose exists, as proved by NMR in D₂O, in five main tautomeric forms in a ratio of about 4:2:2:1:1, only two anomeric 1,4-furanosic forms are present at equilibrium in its 2,6-di-O-benzyl derivative, in ratios ranging from 10:1 to 7:3, depending on the prevalence of D₂O or CD₃CN in the solvent mixture.     

Preparation of L-Lyxo-Hexos-5-Ulose Through C-3 Epimerization of Bis-Glycopyranosides of L-Arabino-Hexos-5-Ulose1

Abstract

The unreported title compound and its 2,6-di-O-benzyl derivative have been prepared from methyl β-D-galactopyranoside through a sequence involving the bisglycoside methyl 2,6-di-O-benzyl-5-O-methoxv-β-D-galactopyranoside 8, the precursor of L-orabino-hexos-5-ulose, that was converted to the L-lyxo series by inversion at C-3. The inversion was achieved in acceptable yields by selective triflation, followed by displacement with benzoate, and by an oxidation/reduction sequence. Whereas 2,5-di-O-benzyl-L-lyxo-hexos-5-ulose exists entirely as a mixture of the two anomeric 1,4-furanosic forms, the unprotected hexos-5-ulose involves at equilibrium in CD₃CN/D₂O at least eight tautomers, one of which is predominant.     

A new synthetic entry to 3-carboxamido-4-carboxylic acid derivatives of isoxazole and pyrazole

Ethyl 2-amino-3-methoxycarbonyl-4-oxo-2-pentenoate (3) reacts with hydroxylamine or hydrazines to give isoxazole and pyrazole ortho-dicarboxylic acid esters 4 and 5, respectively. Partial hydrolysis of diesters 4 and 5 afforded the corresponding dicarboxylic acid monoesters 6 and 7. Amidation of the intermediate acid chlorides 8,9 followed by hydrolysis of 4-methylesters 10, 11 gave the title compounds 1 and 2, respectively.     

Multi-Dimensional Pattern Matching with Dimensional Wildcards: Data Structures and Optimal On-Line Search Algorithms

We introduce a new multidimensional pattern matching problem that is a natural generalization of string matching, a well studied problem[1]. The motivation for its algorithmic study is mainly theoretical. LetA[1:n₁,…,1:n_d] be a text matrix withN = n₁…n_dentries andB[1:m₁,…,1:m_r] be a pattern matrix withM = m₁…m_rentries, whered ≥ r ≥ 1 (the matrix entries are taken from an ordered alphabet Σ). We study the problem of checking whether somer-dimensional submatrix ofAis equal toB(i.e., adecisionquery).Acan be preprocessed andBis given on-line. We define a new data structure for preprocessingAand propose CRCW-PRAM algorithms that build it inO(log N) time withN²/n_maxprocessors, wheren_max = max(n₁,…,n_d), such that the decision query forBtakesO(M) work andO(log M) time. By using known techniques, we would get the same preprocessing bounds but anO((^d_r)M) work bound for the decision query. The latter bound is undesirable since it can depend exponentially ond; our bound, in contrast, is independent ofdand optimal. We can also answer, in optimal work, two further types of queries: (a) anenumerationquery retrieving all ther-dimensional submatrices ofAthat are equal toBand (b) anoccurrencequery retrieving only the distinct positions inAthat correspond to all of these submatrices. As a byproduct, we also derive the first efficient sequential algorithms for the new problem.     

A Convenient ar-SE Laboratory Experiment Avoiding the Use of Sulfuric Acid: the Nitration of Diphenylmethane in Ch2Cl2

The nitration of diphenylmethane to three main isomeric dinitro derivatives, performed with nitric acid in dichloromethane, is proposed as an organic laboratory experiment showing a number of advantages over typical aromatic nitrations in sulfuric acid.     

Ni‐Catalyzed Asymmetric Cycloisomerization of Dienes by Using TADDOL Phosphoramidites

A library of α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol (TADDOL)‐based phosphoramidites has been synthesized and applied in the Ni‐catalyzed cycloisomerization of different dienes. Through the systematic variation of the three structural motifs of the lead structure, that is, the amine moiety, the protecting group, and the aryl substituents, the ligand features could be optimized for the asymmetric cycloisomerization of the model substrate diethyl diallylmalonate. The substrate scope of the new catalytic system was extended to other diallylic substrates, including unsymmetrical dienes. Overall remarkably high activities of up to approximately 13 500 h^?1, very high selectivities toward five‐membered exo‐methylenecyclopentanes, and enantioselectivities of up to 92 % ee have been achieved.