Coordination of azol(in)ium dithiocarboxylate ligands to Au(III): unexpected formation of a novel family of cyclometallated Au(III) complexes, DFT calculations and catalytic studies.

A series of cyclometallated gold(III) complexes 21-27 of general formula [Au(dppta)(azdtc)Cl] (dppta = N,N-diisopropyl-P,P-diphenylphosphinothioic amide-κ2C,S; azdtc = azol(in)ium-2-dithiocarboxylate-κ1S) were prepared and characterized by spectroscopic and diffractometric techniques. Treatment of [Au(dppta)(azdtc)Cl] complexes with methanol led to their quantitative transformation into a novel family of (C^S, S^S)-cyclometallated gold(III) complexes of general formula [Au(dppta)(azmtd)] (azmdt = azol(in)ium-2-(methoxy)methanedithiol-κ2S,S) 28-34. All the [Au(dppta)(azdtc)Cl] complexes 21-27 catalyzed the alkylation of indoles, whereas [Au(dppta)(azmtd)] complexes 28-34 were inactive. Among the synthesized derivatives, complex 22 displayed the highest catalytic activity, leading to a series of functionalized indoles in excellent yields.

Synthesis of Optically Active syn- and anti-Chlorohydrins through a Bienzymatic Reductive Cascade.

A bienzymatic cascade has been designed and optimized to obtain enantiopure chlorohydrins starting from the corresponding 1-aryl-2-chlorobut-2-en-1-ones. For the synthesis of these α-chloroenones, a two-step sequence was developed consisting of the allylation of the corresponding aldehyde with 3-dichloroprop-1-ene, followed by oxidation and further isomerization. The selective cooperative catalytic system involving ene-reductases (EREDs) and alcohol dehydrogenases (ADHs) afforded the desired optically active chlorohydrins under mild reaction conditions in excellent conversions (up to >99%) and selectivities (up to >99:1 diastereomeric ratio (dr), >99% enantiomeric excess (ee)).

Modern Synthetic Methods for the Stereoselective Construction of 1,3-Dienes.

The 1,3-butadiene motif is widely found in many natural products and drug candidates with relevant biological activities. Moreover, dienes are important targets for synthetic chemists, due to their ability to give access to a wide range of functional group transformations, including a broad range of C-C bond-forming processes. Therefore, the stereoselective preparation of dienes have attracted much attention over the past decades, and the search for new synthetic protocols continues unabated. The aim of this review is to give an overview of the diverse methodologies that have emerged in the last decade, with a focus on the synthetic processes that meet the requirements of efficiency and sustainability of modern organic chemistry.

Temperature-Controlled Stereodivergent Synthesis of 2,2'-Biflavanones Promoted by Samarium Diiodide.

In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2'-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2'-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2'-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments.

Unctuous ZrO2 nanoparticles with improved functional attributes as lubricant additives.

One of the main drawbacks in the application of metal-oxide nanoparticles as lubricant additives is their poor stability in organic media, despite the good anti-wear, friction-reducing and high-load capacity properties described for these materials. In this work, we present a novel procedure to chemically cap the surface of ZrO2 nanoparticles (ZrO2NPs) with long hydrocarbon chains in order to obtain stable dispersions of ZrO2NPs in non-aqueous media without disrupting their attributes as lubricant additives. C-8, C-10 and C-16 saturated flexible chains were attached to the ZrO2NP surface and their physical and chemical characterization was performed by transmission electron microscopy, thermogravimetric analysis, attenuated total reflectance Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy and solid-state nuclear magnetic resonance. The dispersion stability of the modified ZrO2NPs in non-aqueous media was studied using static multiple light scattering. Tribological tests demonstrated that dispersions of the long-chain capped ZrO2NPs in base lubricating oils exhibited low friction coefficients and improved the anti-wear properties of the base oil when compared with the raw lubricating oil.

Highly enantioselective synthesis of α-azido-ß-hydroxy methyl ketones catalyzed by a cooperative proline-guanidinium salt system.

The combined activity of (S)-proline and an achiral tetraphenylborate TBD-derived guanidinium salt permits the aldol reaction between azidoacetone and aromatic, or heteroaromatic aldehydes. The α-azido-ß-hydroxy methyl ketones obtained as products can be isolated in good yield, with high diastereo- and enantioselectivity.

Synthesis of enantiopure 2-C-glycosyl-3-nitrochromenes.

A novel methodology has been developed to obtain enantiopure 2-C-glycosyl-3-nitrochromenes. First, (Z)-1-bromo-1-nitroalkenes were prepared from the corresponding sugar aldehydes through a sodium iodide-catalyzed Henry reaction with bromonitromethane followed by elimination of the resulting 1-bromo-1-nitroalkan-2-ols. In the next step, reaction of the sugar-derived (Z)-1-bromo-1-nitroalkenes with o-hydroxybenzaldehydes afforded enantiopure (2S,3S,4S)-3-bromo-3,4-dihydro-4-hydroxy-3-nitro-2H-1-benzopyrans, which, upon SmI2-promoted ß-elimination, yielded chiral enantiopure 2-C-glycosyl-3-nitrochromenes.

General metal-free Baeyer-Villiger-type synthesis of vinyl acetates.

Oxone, a cheap, stable, and nonhazardous oxidizing reagent, transforms α,ß-unsaturated ketones of defined stereochemistry into their corresponding vinyl acetates through a Baeyer-Villiger reaction. This process is general and straightforward, tolerating a wide range of functional groups.

Switching diastereoselectivity in proline-catalyzed aldol reactions.

The choice of the anion of an achiral TBD-derived guanidinium salt, used as cocatalyst for proline, allows reacting cycloketones with aromatic aldehydes and preparing either anti- or syn-aldol adducts with very high enantioselectivity. As a proof of principle, we show how the judicious choice of an additive allows individual access to all possible products, thus controlling the stereochemical outcome of the asymmetric aldol reaction. The origin of the syn diastereoselectivity unfolds from an unusual equilibrium process coupled to the enamine-based catalytic cycle standard for proline.

TBD/Al2O3: a novel catalytic system for dynamic intermolecular aldol reactions that exhibit complex system behaviour.

The heterogeneous system TBD/Al(2)O(3) is an efficient catalyst for the intermolecular aldol reaction between ketones and aromatic aldehydes. This system operates with low catalysts loading (10%), in water or organic solvents, and with short reaction times. The desired aldol products are rendered cleanly. Experiments confirmed that this aldol protocol is reversible, and allowed for the preparation of dynamic combinatorial libraries (DCLs) of interconverting aldols. Analysis of these DCLs showed up how properties such as diastereoselectivity can emerge unpredictably from the library when it is considered as a whole.

Chromium-mediated stereoselective synthesis of carbohydrate-derived (E)-α,ß-unsaturated esters or amides.

A chromium-mediated novel synthesis of carbohydrate-derived di- and trisubstituted (E)-α,ß-unsaturated esters or amides from a range of dichloroesters or amides and a variety of sugar aldehydes is reported. The process took place with total stereoselectivity and in high yields. A mechanism based on a sequential chromium-promoted aldol-type reaction and a completely stereoselective ß-elimination reaction is proposed to explain these results.

Direct aldol reactions catalyzed by a heterogeneous guanidinium salt/proline system under solvent-free conditions.

The combined activity of (S)-proline and an achiral cocatalyst (a TBD-derived guanidinium salt) allow direct aldol reactions to be carried out with high diastereoselectivity and enantioselectivity under solvent-free conditions with a rather simple reaction setup where stirring is not required.

Stereospecific and highly stereoselective cyclopropanation reactions promoted by samarium.

Samarium metal and samarium diiodide have become important tools as selective cyclopropanating agents in organic synthesis due to their high chemo- and stereoselectivity. Therefore, Sm and SmI(2) are the ideal reagents to prepare cyclopropane derivatives. This tutorial review highlights C-C multiple bond cyclopropanation processes promoted by samarium or samarium diiodide.

Sequential synthesis of (E)-alpha,beta-unsaturated primary amides with complete stereoselectivity.

A novel, efficient, and totally stereoselective synthesis of (E)-alpha,beta-unsaturated primary amides is reported. This process is consistent with a SmI(2)-mediated sequential reaction of an unmasked samarium chloroacetamide enolate with an aldehyde, followed by a beta-elimination to produce (E)-alpha,beta-unsaturated primary amides in good yields.

Total regioselective transformation of aromatic aziridine 2-carboxamides into 2-aminoamides promoted by active manganese.

A novel, totally regioselective transformation of aromatic N-4-methoxyphenylaziridine 2-carboxamides into 2-aminoamides promoted by active manganese (Mn*) is reported. alpha-Amino ketones can be readily obtained by reaction of morpholine-derived 2-aminoamides with organolithium compounds.

Addition reactions of chloro- or iodomethyllithium to imines. Synthesis of enantiopure aziridines and beta-chloroamines.

We report a novel, simple, and efficient synthesis of aziridines and 1-chloroalkan-2-amines by the reaction of imines derived from various aldehydes and p-toluenesulfonamide or benzenesulfonamide with iodo- or chloromethyllithium, respectively. Both halogenated anions were generated in situ by treatment of diiodo- or chloroiodomethane with methyllithium at -78 or 0 degrees C. The reaction of in situ generated iodo- or chloromethyllithium could also be performed from chiral 2-aminoaldimines to yield enantiopure aziridines or (2S,3S)-2,3-diamino-1-chloroalkanes with high stereoselectivity.

General, stereoselective synthesis of (Z)-beta,gamma-unsaturated nitriles promoted by samarium diiodide.

A method to obtain (Z)-beta,gamma-unsaturated nitriles in high or good yields and with moderate or high stereoselectivity is described. The products were achieved through the photoinduced metalation of 3-acetoxy-4-chloronitriles with SmI2. The starting compounds were readily prepared, and a mechanism is proposed to explain this stereoselective beta-elimination reaction.

Addition reactions of iodomethyllithium to imines. A direct and efficient synthesis of aziridines and enantiopure amino aziridines.

An efficient and general synthesis of aziridines by the reaction of imines derived from p-toluenesulfonamides with in situ generated iodomethyllithium, with a simple and rapid experimental protocol, is reported for the first time. The reaction with the chiral aldimine derived from phenylalaninal allowed access to (2R,1'S)-2-(1'-aminoalkyl)aziridine with very high diastereoselectivity, in enantiopure form. A mechanism to explain this novel reaction is proposed.

Recent synthetic applications of manganese in organic synthesis.

While the organometallic compounds derived from many metals have found a broad application in organic synthesis, the use of organomanganese compounds has only recently been developed due to the passivity exhibited by commercial Mn in the direct metalation of organic compounds. In this Concept article, we highlight the potential of manganese and its organometallic compounds in organic synthesis by illustration of the studies previously reported by others and our laboratory in this field. Based on the transformations reported herein, organomanganese compounds could become important tools in the future of the organic synthesis, due to their high selectivity.