The Antitumoral Effect In Ovo of a New Inclusion Complex from Dimethoxycurcumin with Magnesium and Beta-Cyclodextrin.

Breast cancer is one of the leading causes of death in the female population because of the resistance of cancer cells to many anticancer drugs used. Curcumin has cytotoxic activities against breast cancer cells, although it has limited use due to its poor bioavailability and rapid metabolic elimination. The synthesis of metal complexes of curcumin and curcuminoids is a relevant topic in the search for more active and selective derivatives of these molecular scaffolds.

First Gallium and Indium Crystal Structures of Curcuminoid Homoleptic Complexes: All-Different Ligand Stereochemistry and Cytotoxic Potential.

The crystal structure determination of metal complexes of curcuminoids is a relevant topic to assess their unequivocal molecular structure. We report herein the first two X-ray crystal structures of homoleptic metal complexes of a curcuminoid, namely Dimethoxycurcumin (DiMeOC), with gallium and indium. Such successful achievement can be attributed to the suppression of interactions from the phenolic groups, which favor an appropriate molecular setup, rendering Dimethoxycurcumin gallium ((DiMeOC)-Ga) and Dimethoxycurcumin indium ((DiMeOC)-In) crystals.

The Homoleptic Curcumin-Copper Single Crystal (ML): A Long Awaited Breakthrough in the Field of Curcumin Metal Complexes.

The first single crystal structure of the homoleptic copper (II) ML complex (M=Cu (II), L = curcumin) was obtained and its structure was elucidated by X-ray diffraction showing a square planar geometry, also confirmed by EPR. The supramolecular arrangement is supported by C-H···O interactions and the solvent (MeOH) plays an important role in stabilizing the crystal packing Crystallinity was additionally assessed by XRD patterns. The log P value of the complex (2.

Stereocontrolled Addition of Scrambling -Sulfinyl Carbanions: Easy Access to Homopropargylamines and α-Allenylamines.

An unprecedented behavior of -sulfinylpropargyl carbanions in the presence of optically active sulfinylimines affords two different families of compounds: this peculiar chemodivergency is importantly affected by the nature of the employed base, and assisted by the configuration of the electrophile, displaying no alteration in the stereocontrol of both reactions. α-Allenylamines are formed exclusively, using -sulfinyl aldimines as electrophiles, while homopropargylamines result when -sulfinyl aldimines are employed.

Asymmetric [2,3]-Wittig Rearrangement: Synthesis of Homoallylic, Allenylic, and Enynyl α-Benzyl Alcohols.

A highly stereoselective [2,3]-Wittig rearrangement of allylic and propargylic ethers controlled by a chiral sulfoxide moiety is presented. The activation provided by the sulfoxide at the remote ortho position allows the rearrangement of less-activated and unexplored benzylic carbanions. Thus, this general methodology gives access to the asymmetric synthesis of homoallylic, enynyl, and allenylic α-benzyl alcohol derivatives.

Asymmetric Synthesis of Secondary and Tertiary Propargylic Alcohols by Umpolung of Acetylenic Sulfones and ortho-Sulfinyl Carbanions.

The generation of diastereomerically enriched secondary benzyl propargyl alcohols by the asymmetric addition of ortho-sulfinylbenzyl carbanions to sulfonylacetylene derivatives via formation of a Csp-Csp bond is described. This reaction proceeds through an unusual α-attack (anti-Michael addition) of the ortho-sulfinylbenzyl carbanions, followed by elimination of the arylsulfonyl moiety. The scope of this alkynylation reaction is also discussed.

1,2-Dimeth-oxy-4-methyl-3-[(S)-p-tolyl-sulfin-yl]benzene.

In the title compound, C(16)H(18)O(3)S, the dihedral angle between the benzene rings is 75.48 (8)°. The absolute configuration at the stereogenic S-atom center was determined as S.

Asymmetric synthesis of (S)-(-)-xylopinine. Use of the sulfinyl group as an ipso director in aromatic SE.

Optically pure (S)-(-)-xylopinine 2 was prepared in three steps in 52% overall yield. Thus, condensation of the carbanion derived from (S)-4 with the (S)-(E)-sulfinylimine 5 gave a 2:1 mixture of tetrahydroisoquinolines 6a and 6b, differing only in configuration at sulfur. N-Desulfinylation of this mixture gave the diastereomeric sulfoxides which, without separation, were converted into (S)-(-)-xylopinine (2) with loss of the sulfinyl moieties under Pictet-Spengler conditions.

Methyl sulfinates as electrophiles in Friedel-Crafts reactions. Synthesis of aryl sulfoxides.

The Friedel-Crafts reaction of methyl alkyl- and arylsulfinates with aromatic systems, activated by one or more electron-donating substituents (OH, OMe, NHR, NR(2)), provides alkyl aryl and diaryl sulfoxides under mild conditions and in moderate to good yields. The very high regioselectivity usually observed in these sulfinylation reactions is rationalized on the basis of a Wheland intermediate having a trigonal bypyramidal structure in which steric and electronic interactions are significant factors strongly destabilizing the attack to the ortho positions.