1. DABSO as a SO2 gas surrogate in the synthesis of organic structures
Mehri Seyed Hashtroudi, Vaezeh Fathi Vavsari, Saeed Balalaie Org Biomol Chem. 2022 Mar 16;20(11):2149-2163.doi: 10.1039/d1ob02199k.
1,4-Diazabicyclo[2.2.2]octane bis(sulfur dioxide), DABCO·SO2, or DABSO, a bench-stable colorless solid, is industrially produced by the reaction of DABCO with condensed and bubbled sulfur dioxide gas at a low temperature. However, in some cases, it could catalyze organic reactions. DABSO is mostly used as a surrogate of gaseous sulfur dioxide to react with organic substrates, including Grignard reagents, aryl or alkyl halides, boronic acids, various amines, diazonium salts, carboxylic acids, heterocycles, acrylamides, alkenes, alkynes, and β-alkynyl ketones, through one-pot protocols, annulation, or coupling reactions. Most of these synthetic reactions proceed via the formation of a sulfinate radical or anion. Using DABSO as a reagent, various simple to complex structures can be constructed, such as metal sulfinates, sulfonyl fluorides, sulfonamides, sulfonohydrazides, sulfonic esters, sulfonic thioesters, and sulfones. In this review, we want to investigate mechanistically the role of DABSO in organic synthesis.
2. Bis-Thiourea Chiral Sensor for the NMR Enantiodiscrimination of N-Acetyl and N-Trifluoroacetyl Amino Acid Derivatives
Alessandra Recchimurzo, Federica Balzano, Gloria Uccello Barretta, Luca Gherardi J Org Chem. 2022 Sep 16;87(18):11968-11978.doi: 10.1021/acs.joc.2c00814.Epub 2022 Sep 5.
A C2-symmetrical bis-thiourea chiral solvating agent (CSA), TFTDA, for NMR spectroscopy has been obtained by reacting (1R,2R)-1,2-bis(2-hydroxyphenyl)ethylenediamine and 3,5-bis(trifluoromethyl)phenyl isothiocyanate. TFTDA shows remarkable propensity to enantiodiscriminate N-trifluoroacetyl (N-TFA) and N-acetyl (N-Ac) derivatives of amino acids with free carboxyl functions, with the co-presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as the third achiral additive, which is needed for substrate solubilization. TFTDA shows enhanced enantiodiscriminating efficiency in comparison with the corresponding monomeric counterpart, TFTMA, pointing out cooperativity between its two symmetrical entities. A wide range of amino acid derivatives have been efficiently enantiodiscriminated in CDCl3, with high enantioresolution quotients, which guarantee high quality in applications devoted to the quantification of enantiomers. High enantiodiscriminating efficiency is maintained also in diluted 5 mM conditions or in the presence of sub-stoichiometric amounts of CSA (0.3 equiv). The role of phenolic hydroxyls in the DABCO-mediated interaction mechanism between TFTDA and the two enantiomeric substrates has been pointed out by means of diffusion-ordered spectroscopy (DOSY) and rotating frame Overhauser effect spectroscopy (ROESY) experiments. A conformational model for both the CSA and its diastereomeric solvates formed with the two enantiomers of N-acetyl leucine has also been conceived on the basis of ROE data in order to give a chiral discrimination rationale.
3. Crystallographic identification of a series of manganese porphyrin complexes with nitrogenous bases
Nicole Lahanas, Pavel Kucheryavy, Roger A Lalancette, Jenny V Lockard Acta Crystallogr C Struct Chem. 2019 Mar 1;75(Pt 3):304-312.doi: 10.1107/S2053229619001232.Epub 2019 Feb 13.
Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme-based protein systems, but also the catalytic properties of porphyrin-based reaction sites in other biomimetic synthetic support environments. Unlike iron porphyrin complexes, little is known about the axial ligation behavior of Mn porphyrins, particularly in the solid state with Mn in the +3 oxidation state. Here, we present the syntheses and crystal and molecular structures of three new high-spin manganese(III) porphyrin complexes with the different amine-based axial ligands imidazole (im), piperidine (pip), and 1,4-diazabicyclo[2.2.2]octane (DABCO), namely bis(imidazole)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride chloroform disolvate, [Mn(C44H28N4)(C3H4N2)2]Cl·2CHCl3 or [Mn(TPP)(im)2]Cl·2CHCl3 (TPP = 5,10,15,20-tetraphenylporphyrin), (I), bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride, [Mn(C44H28N4)(C5H11N)2]Cl or [Mn(TPP)(pip)2]Cl, (II), and chlorido(1,4-diazabicyclo[2.2.2]octane)(5,10,15,20-tetraphenylporphyrin)manganese(III)-1,4-diazabicyclo[2.2.2]octane-toluene-water (4/4/4/1), [Mn(C44H28N4)Cl(C6H12N2)]·C6H12N2·C7H8·0.25H2O or [Mn(TPP)Cl(DABCO)]·(DABCO)·(toluene)·0.25H2O, (IV). A fourth complex, chlorido(pyridine)(5,10,15,20-tetraphenylporphryinato)manganese(III) pyridine disolvate, [Mn(C44H28N4)Cl(C5H5N)]·2C5H5N or [Mn(TPP)Cl(py)]·2(py), (III), acquired using different crystallization methods from published data, is also reported and compared to the previous structures.
