Chiral phosphine oxide BINAPO as a Lewis base catalyst for asymmetric allylation and aldol reaction of trichlorosilyl compounds

Chiral phosphine oxide BINAPO, which was readily prepared from chiral phosphine BINAP, exhibited good catalytic activities in the reaction of trichlorosilyl compounds via hypervalent silicate intermediates. The allylation of aldehydes with allyltrichlorosilanes in the presence of a catalytic amount of BINAPO gave the allylated adducts in good enantioselectivities (up to 79% ee) wherein a combination of diisopropylethylamine and tetrabutylammonium iodide as additives was crucial to accelerate the catalytic cycle. ³¹P NMR analysis of the phosphine oxide suggested that the amine promoted the dissociation of phosphine oxide from silicon atom. BINAPO also promoted the enantioselective aldol reaction of aldehydes with trichlorosilyl enol ethers in the presence of diisopropylethylamine as an additive to afford the corresponding aldol adducts in high diastereo- and enantioselectivities (up to syn/anti=1/25, 96% ee (anti)).     

Stereoselective Wittig olefination reactions employing a novel ortho-P-aryl alkoxide effect

Non-stabilized ortho-P-alkoxy-substituted ylides react with aromatic and aliphatic aldehydes providing (E)-olefins with high stereocontrol, also allowing easy phosphine oxide removal in certain cases.     

Biheteroaromatic diphosphine oxides-catalyzed stereoselective direct aldol reactions

A highly stereoselective direct aldol condensation of ketones to aromatic aldehydes was realized; the trichlorosilyl enolether generated in situ in the presence of tetrachlorosilane is activated by catalytic amounts of an enantiomerically pure biheteroaromatic phosphine oxide to react with aldehydes, coordinated as well as activated by the chiral cationic hypervalent silicon species. This Lewis acid-mediated Lewis base-catalyzed transformation allowed, starting from two carbonyl compounds, to directly synthesize β-hydroxy ketones generally with high anti stereoselectivity and up to 93% ee for the anti isomer.     

CuO nano-particles supported on silica,a new catalyst for facile synthesis of benzimidazoles,benzothiazoles and benzoxazoles

A facile synthetic route for benzimidazoles, benzothiazoles and benzoxazoles comprising the reaction of corresponding o-phenylenediamine, o-aminothiophenol and o-aminophenol with various aldehydes using silica supported nano-copper (II) oxide as a catalyst has been described. The catalyst exhibited a clean reaction profile with excellent yields in a short reaction time. The catalyst can be recycled effectively after use.     

Organocatalytic asymmetric cascade cyclization reaction of o-hydroxy cinnamaldehydes with diphenylphosphine oxide

A highly stereoselective asymmetric cascade cyclization reaction between o-hydroxycinnamaldehydes and diphenylphosphine oxide has been achieved with 84%-99% ee and 7:1-20:1 dr under the catalysis of L-prolinol silyl ether.     

Catalytic asymmetric methallylation and propargylation of aldehydes with bis(((S)-binaphthoxy)(isopropoxy)titanium) oxide

New and highly efficient enantioselective methallylation and propargylation of achiral aldehydes with methallyltributyltin and allenyltributyltin, respectively, can be achieved with high enantioselectivity under the influence of chiral bis(((S)-binaphthoxy)(isopropoxy)titanium) oxide as catalyst.     

Synthesis of 3,3,3-trifluoroprop-1-enyl compounds from some enolizable aldehydes

2,2,2-Trifluoroethyldiphenylphosphine oxide [Ph₂P(O)CH₂CF₃] (2) is known to give no Horner reaction product with enolizable aldehydes. We found, however, that some enolizable aldehydes such as N-Boc-pyrrolidine-2-aldehyde (9) gave the expected 3,3,3-trifluoroprop-1-enyl compounds by reaction with 2. The products could be further transformed to some 2,2,2-trifluoroethyl-substituted nitrogen-containing heterocycles by using radical cyclization or Heck reaction.     

Direct asymmetric aldol reactions catalyzed by nanocrystalline copper(II) oxide

The direct asymmetric aldol reactions of aromatic and heteroaromatic aldehydes with acetone to afford chiral β-hydroxy carbonyl compounds in good yields and good to moderate enantioselectivities are realized using nanocrystalline copper(II) oxide in the presence of (1S,2S)-(−)-1,2-diphenylethylenediamine at −30 °C. The catalyst can be reused for four cycles with consistent activity and enantioselectivity.     

One-pot solid phase synthesis of (E)-nitroalkenes

An efficient one-pot protocol for the synthesis of (E)-nitroalkenes by reaction of aldehydes and nitroalkanes in the presence of polymer-bound triphenylphosphine, iodine and imidazole is described. Although the reaction works with similar efficiency with triphenylphosphine and its polymer-bound version, easy removal of the unwanted polymer-bound triphenylphosphine oxide and its recovery as triphenylphosphine provide the edge for practical application of the method.     

Ceria/vinylpyridine polymer nanocomposite: an ecofriendly catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones

The three-component condensation of aldehydes, β-ketoesters and urea has been carried out in water using ceria (cerium oxide, CeO₂) nanoparticles supported on poly(4vp-co-dvb) as a catalyst for the preparation of 3,4-dihydropyrimidin-2(1H)-ones in good yields. The catalyst was recovered easily and reused without loss of its activity.     

Ligand enabled none-oxidative decarbonylation of aliphatic aldehydes

Decarbonylation of aldehydes is a basic organic transformation, which has been developed for more than six-decade. However, as comparing to well-studied aromatic aldehydes, fewer examples for catalytic decarbonylation of aliphatic aldehydes were reported, mainly on simple or special substrates. For α-bulky or highly functionalized ones, stoichiometric Rh(I) were usually required for decent yields. Herein, we present a rare example of Ir(I)-catalyzed direct decarbonylation of α-quaternary aldehydes with broad substrate scope and good functional group compatibility via judicious selection of ligand. The α-chirality is memorized in this decarbonylation process. In addition, we report a broad-spectrum decarbonylation of α-secondary and α-tertiary aldehydes containing multifunctional groups with an improved Rh(I)/DPPP recipe. Finally, we realized selective decarbonylation of α-tertiary aldehydes in the presence of α-quaternary one via the reactivity differences.     

Enantioselective addition of trimethylsilyl cyanide to aldehydes catalysed by bifunctional BINOLAM-AlCl versus monofunctional BINOL-AlCl complexes

A highly enantioselective cyanation of aldehydes takes place by using a bifunctional catalyst derived from 3,3′-bis(diethylaminomethyl) substituted binaphthol (BINOLAM) and dimethylaluminium chloride. The addition is of wide scope and runs best in toluene at temperatures ranging from −20 to −40 °C, in the presence of 4 Å MS and triphenylphosphine oxide as additives. The (R)- or (S)-cyanohydrins result when using (S)- or (R)-BINOLAM-AlCl complexes, respectively. The valuable ligand can be recovered by simple extractive work-up and recycled without loss of efficiency (both in terms of chemical and stereochemical yields). This methodology is applied to the Shibasaki synthesis of epothilone A. All the evidence available for the BINOLAM-AlCl enantioselective addition of TMSCN to aldehydes call for the intervention of a hydrocyanation reaction, addition of a catalytic amount of hydrogen cyanide, generated in situ, to an aldehyde, followed by O-silylation. In order to determine the role of the basic amino groups of BINOLAM, comparative studies are carried out with the monofunctional 1,1′-binaphthol-derived complex BINOL-AlCl.     

A versatile route to the synthesis of 1-substituted β-carbolines by a single step Pictet-Spengler cyclization

A one-step conversion of l-tryptophan and activated aldehydes (1,2-dicarbonyl compounds) directly to 1-substituted β-carbolines without formation of the tetrahydro derivatives under modified Pictet-Spengler conditions was described. Moreover, a practical application for the synthesis of a natural 1-substituted β-carboline, luzongerine A, isolated from Illigera luzonensis was also successfully carried out utilizing this protocol. The effects of synthetic compounds 11 and 11a on nitric oxide (NO) production in LPS/IFN-γ stimulated RAW 264.7 macrophage cells were evaluated in vitro. They displayed significant dose-dependent inhibition of inducible nitric oxide synthase (iNOS).     

Chiral pyridine N-oxides derived from monoterpenes as organocatalysts for stereoselective reactions with allyltrichlorosilane and tetrachlorosilane

The synthesis of enantiomerically pure C₂-symmetric dipyridylmethane ligands and related N,N′-dioxides is reported. A procedure for the synthesis of a few new enantiomerically pure C₂-symmetric pyridine N-oxides and the preparation of four pyridine N-oxides with oxygen and nitrogen atoms as further coordinating elements in the heterocycle framework is described. All compounds were prepared from naturally occurring monoterpenes. These new compounds were assessed as organocatalysts in two different reactions, namely the allylation of aldehydes with allyltrichlorosilane that afforded homoallylic alcohols in good yields and up to 85% ee and the stilbene oxide opening by the addition of tetrachlorosilane that gave chlorohydrin in quantitative yield and up to 70% ee.     

Ruthenium(II)-salen complexes-catalyzed olefination of aldehydes with ethyl diazoacetate

Several salen-ruthenium(II) complexes, which are derived from commercial ligands or simply ethylenediamine, can be successfully applied as catalysts for the olefination of a broad variety of aldehydes. Depending on the electron richness of the applied aldehydes, good to very good olefin yields and high E:Z selectivities are reached at 60 or 80 °C reaction temperature with ethyl diazo acetate being the reaction partner. The reaction rate depends on the electron donor capabilities of the aldehydes. Electron poor aldehydes undergo faster reactions than electron rich aldehydes, but both electron rich and bulky aldehydes can be transformed to corresponding olefins in very good yields and high E-selectivity.     

Studies on the role of Lewis basicity of the aldehydes utilized in the enantioselective Mukaiyama aldol reaction promoted by chiral 1,3,2-oxazaborolidin-5-ones

N-Tosyl-2-1,3,2-oxazaborolidin-5-one 1 was used to probe the role of the Lewis basicity of aldehydes utilized in Mukaiyama aldol reactions promoted by oxazaborolidin-5-ones. Eight aldehydes were each allowed to undergo a Mukaiyama aldol reaction with ketene silyl acetal derived from methyl isobutanoate. Lewis basicity of the aldehydes was determined computationally. The best results were obtained with isobutyl aldehyde and 3,4,5-trimethoxy benzaldehyde (91% and 85% ee). The best fit of ee as a function of Lewis basicity gave a correlation of R²=0.79 [when two ortho-substituted aldehydes were excluded] suggesting that Lewis basicity of O_CHO can play a role in reactions of aldehydes promoted by 1.     

Cyanosilylation of Aldehydes and Ketones Catalyzed by Nanocrystalline Magnesium Oxide

Abstract

Cyanosilylation of various aldehydes and ketones with TMSCN proceeded smoothly under mild conditions to give the corresponding cyanohydrin trimethylsilyl ethers in the presence of nanocrystalline magnesium oxide. The cyanohydrin trimethylsilyl ethers of aldehydes produced cyanohydrins in good to high yields on treatment with 2 N HCl. ²⁹Si NMR spectral evidence proved that the reaction proceeds through the hypervalent silicate species by coordination to O^2?/O^? (Lewis basic site) of nanocrystalline magnesium oxide.     

N-Heterocyclic carbene-catalyzed oxidations

N-Heterocyclic carbenes catalyze the oxidation of allylic and benzylic alcohols as well as saturated aldehydes to esters with manganese(IV) oxide in excellent yields. A variety of esters can be synthesized, including protected carboxylates. The oxidation proceeds under mild conditions, with low loadings of a simple triazolium salt pre-catalyst in the presence of base. Substrates containing potentially epimerizable centers are oxidized while preserving stereochemical integrity. The acyl triazolium intermediate generated under catalytic conditions can be employed as a chiral acylating agent in the desymmetrization of meso-diols.     

Influence of α-methyl substitution of proline-based organocatalysts on the asymmetric α-oxidation of aldehydes

The direct asymmetric organocatalytic α-oxidation of aldehydes using trans-2-(p-methylphenylsulfonyl)-3-phenyloxaziridine is reported. This method affords the S isomer of α-hydroxy aldehydes, thereby complementing the selectivity for the R isomer observed using the two-step nitrosobenzene method. Use of α-methylproline and α-methylproline tetrazole significantly increases the enantioselectivity observed for the α-oxidation of aldehydes compared to analogous unsubstituted organocatalysts.     

Fluorimetric determination of aromatic aldehydes with 2,2'-dithiobis(1-aminonaphthalene)

A sensitive fluorimetric method for the determination of aromatic aldehydes is based on their reaction in dilute sulfuric acid with a new reagent, 2,2'-dithiobis(l-amino-naphthalene) in the presence of tri-n-butylphosphine, sodium sulfite and sodium phosphite at ambient temperature. The fluorescences produced are fairly characteristic of individual aldehydes. The method is extremely selective for aromatic aldehydes and very sensitive, especially for p-hydroxybenzaldehyde, o-methoxybenzaldehyde, p-methoxybenzaldehyde and p-tolualdehyde which can be determined at concentrations of as little as 3–5 ng ml^-1.