Jacques Maddaluno

Oxidative Neutralization of Mustard-Gas Simulants in an On-Board Flow Device with In-Line NMR Monitoring

The fast and effective neutralization of the mustard-gas simulant 2-chloroethyl ethyl sulfide (CEES) using a simple and portable continuous flow device is reported. Neutralization takes place through a fully selective sulfoxidation by a stable source of hydrogen peroxide (alcoholic solution of urea-H2 O2 adduct/MeSO3 H freshly prepared). The reaction progress can be monitored with an in-line benchtop NMR spectrometer, allowing a real-time adjustment of reaction conditions. Inherent features of millireactors, that is, perfect control of mixing, heat and reaction time, allowed the neutralization of 25u2005g of pure CEES within 46u2005minutes in a 21.5u2005mL millireactor (tR =3.9u2005minutes). This device, which relies on affordable and nontoxic reagents, fits into a suitcase, and can be deployed by police/military forces directly on the attack site.

Aza-Michael Access to Fluoroalkylidene Analogues of Biomolecules

The synthesis of fluoroaminosulfones derived from piperidine and nucleic bases followed by the study of their chemical behavior in the modified Julia reaction are described. The resulting aminosulfones open a straightforward access to a series of new fluorinated biomolecules including a potent DPP-II inhibitor and acyclonucleoside analogues as potential enzyme inhibitors.

1-(Phenylthio)- and 1-(phenylsulfoxide)-4-alkoxy-butadienes, a new class of chiral dienes.

Abstract Trans-acetalization of the methyl acetal of 3-methyl-4-(phenylthio)-but-2-enal 2a in acidic medium leads to the expected trans-acetals 2b–f or their γ-elimination products (i.e. 4-alkoxy-2-methyl-1-(phenylthio)buta-1,3-dienes 4 ), depending on the nature of the selected alcohol. Both types of compounds may be easily oxidized into the expected sulfoxides 6 . The menthyloxy and phenyl-8-menthyloxy sulfides 4b,c and sulfoxides 6b,c have been prepared.

Synthesis and Diels-Alder reactivity of functionalized aminodienes and bis-dienes

Abstract γ-Amino α,β-unsaturated dimethyl acetals are direct precursors of (E)-1-methoxy-2-methylamino-1,3-butadiene and of the corresponding bis-dienes, which are useful partners in cycloadditions.

Chiral Lithium Amides: Tuning Asymmetric Synthesis on the Basis of Structural Parameters

An overview on the structural arrangements adopted by Chiral Lithium Amides (CLAs), alone or in mixed complexes, is presented. These species are important reagents for asymmetric synthesis and understanding their organization is essential to improve their design and the reaction conditions.

“On water” reaction of deactivated anilines with 4-methoxy-3-buten-2-one, an effective butynone surrogate

Poorly nucleophilic aromatic amines (nitroanilines, chloroanilines, etc.) react readily and selectively with trans-4-methoxy-3-buten-2-one, a convenient, effective and inexpensive surrogate for 3-butyn-2-one, to afford (Z)-enaminones. The efficiency of the reaction mostly lies in the use of water as a solvent, which enhances the reaction rate by a 45 to 200-fold factor with regard to other media.

2D 7Li Ultrafast CT-COSY: a new tool for the rapid measurement of tiny homonuclear lithium scalar couplings

The measurement of small homonuclear 2J7Li-7Li scalar couplings relying on constant time (CT) COSY NMR suffers from strong time limitations. We describe the first Ultrafast CT COSY experiment on lithium 7, which provides a considerable acceleration in the study of the aggregation state and dynamics of n-BuLi/MeLi complexes.

Access to Anti or Syn 2-Amino-1,3-diol Scaffolds from a Common Decarboxylative Aldol Adduct

A straightforward synthetic pathway allowing the access to anti or syn 2-amino-1,3-diol scaffolds is presented. The strategy relies on a diastereoselective organocatalyzed decarboxylative aldol reaction of a N-Boc-hemimalonate that is easily formed from commercial N-Boc-diethyl malonate. Although this method has been optimized previously with the N-Bz-hemimalonate analogue, this key step was reinvestigated with the N-Boc derivative to improve the required reaction time, the yield, and the diastereoselectivity. The new conditions enhance this transformation, and quantitative yields and anti/syn ratios up to 96:4 can be obtained. The anti aldol product was easily isolated in pure form and then taken forward as the key precursor in the preparation of both a set of ten N-/O-alkylated anti 2-amino-1,3-diol derivatives and the syn congeners.