A new route of the reaction of EtAlCl2 with α-olefins catalyzed by Ti complexes

A new method for the synthesis of dialkyl(ethyl)alanes by the reaction of EtAlCl₂ with -olefins in the presence of Mg and a catalytic amount of Cp₂TiCl₂ (Ti(OPrⁱ)₄, Ti(OBuⁿ)₄) in THF was developed.     

Synthesis of trialkylaluminum derivatives by the reaction of non-solvated aluminum hydride with α-olefins

Hydroalumination of -olefins by non-solvated polymeric aluminum hydride (AlH₃) _n occurs at 120—140 °C. Mechanochemical activation accelerates this reaction. The addition of catalytic amounts of the prepared R₃Al forms to the reaction system decreases the temperature of the process to 90—100 °C. The greatest initiation effect is observed when ate-complexes of the MAlR₄ type (M = Li, Na) are used: the reaction occurs with a higher rate already at 60—90 °C affording R₃Al free of admixtures of carbalumination products and dimers of -olefins.     

An unusual reaction of α-alkoxyphosphonium salts with Grignard reagents under an O2 atmosphere

An unusual and novel reaction of α-alkoxyphosphonium salts, generated from O,O-acetals and Ph(3)P, with Grignard reagents under an O(2) atmosphere afforded alcohols in moderate to high yields. It was clarified by isotopic labelling experiments that the reaction proceeded via a novel radical pathway.     

Cp2TiCl2-Catalyzed hydroalkylation of α-olefins with ButBr—Et3Al

The reactions of olefins with alkyl halides and Et₃Al in the presence of catalytic amounts of Cp₂TiCl₂ were studied. Unbranched -olefins of the aliphatic series underwent hydroalkylation under the action of tert-butyl bromide to form 2,3-dimethylalkanes.     

One-step synthesis of trialkylaluminum derivatives and dialkylaluminum hydrides by the reaction of alkaline metal aluminum hydrides with α-olefins and alkylaluminum chlorides

A simple method for one-step preparation of the organoaluminum compounds R₃Al, R₂AlH, R₂R"Al, and RR"AlH by the reaction of MAlH₄ (M = Li, Na) with R₂AlHal (Hal = Cl, Br) and -olefins (3-methylbut-1-ene, hex-1-ene, oct-1-ene, dec-1-ene) was proposed.     

Synthesis and reactions of metallocycles. 6. Stereoselective synthesis of 3,4-dialkyl-substituted aluminocyclopentanes by cyclometallation of α-olefins using trialkylalanes in the presence of Cp2ZrCl2

An efficient method has been developed for the synthesis of a new class of organoaluminum compounds, trans-3,4-dialkyl-substituted aluminocyclopentanes, via the cyclometallation of -olefins using R₃A1 in the presence of catalytic amounts of Cp₂ZrCl₂. Hydrolysis, deuterolysis, and oxidation of the resulting aluminocy-clopentanes generate the corresponding transformation products having exclusively the threo-configuration.For previous communication see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1141–1144, May, 1991.     

Direct asymmetric aldol reaction of acetone with α-ketoesters catalyzed by primary-tertiary diamine organocatalysts

Novel primary-tertiary diamine organocatalysts derived from l-serine were utilized to promote enantioselective aldol reaction of acetone with α-ketoesters. The desired products were obtained in high yields and with good to excellent enantioselectivities (up to 95% ee).     

An efficient hydrocyanation of α, β-unsaturated diesters with TMSCN catalyzed by MgI2 etherate

Abstract

A mild, efficient and highly regioselective addition of trimethylsilyl cyanide (TMSCN) to α,β-unsaturated diesters has been achieved by using MgI₂ etherate as catalyst under solvent-free conditions. This protocol provides the corresponding β-cyano esters in high yields.     

A new reaction of diazomethane with norbornyl α-diketones

A new reaction of diazomethane with norbornyl α-diketones in MeOH as solvent leading regioselectively to ketals is described. The mechanistic details of this intriguing reaction were investigated employing d₄-MeOH, EtOH and d₆-EtOH. The surprising observation of complete deuterium incorporation in the diazomethane-derived methoxy group was accounted for by sequential deuterium exchange between the initially formed hemiketal d₄-18 and diazomethane in the presence of d₄-MeOH as solvent.     

Synthesis of novel zerumbone derivatives via regioselective palladium catalyzed decarboxylative coupling reaction: a new class of α-glucosidase inhibitors

A new strategy for the synthesis of novel zerumbone derivatives via a regioselective palladium catalyzed decarboxylative coupling reaction using arene carboxylic acids is described. The current methodology involves the repositioning of endocyclic double bond to exocyclic double bond of zerumbone. Preliminary in vitro analysis revealed that most of the newly synthesized derivatives are potent α-glucosidase enzyme inhibitors.     

Enantioselective α-hydroxylation of β-keto esters catalyzed by chiral S-timolol derivatives

A screen of aryloxy aminopropanol organocatalysts derived from the β-blocker inhibitor S-timolol determined the most active catalyst of asymmetric α-hydroxylation of β-keto esters. (R)-1-(tert-butylamino)-3-(3,4,5-trimethoxyphenoxy) propan-2-ol (3k) was the most effective derivative, enantioselectively catalyzing α-hydroxylation of β-keto esters using tert-butyl hydroperoxide as the oxidant in hexane to afford the corresponding products in excellent yield and with good enantioselectivity (up to 96% yield, 88% ee).     

Asymmetric aza-Henry reaction with α-substituted nitroacetates catalyzed by a bifunctional thiourea-guanidine catalyst

The asymmetric aza-Henry reaction of α-substituted nitroacetates and N-Boc imines was achieved with a new-type thioureaguanidine bifunctional organocatalyst.The novel transformations exhibited high diastereoselectivities,and the adducts bearing adjacent quaternary and tertiary chiral centers were generally obtained in moderate to good enantioselectivities(up to 88%ee).     

Solvent-free sonochemical kabachnic-fields reaction to synthesize some new α-aminophosphonates catalyzed by nano-BF3•SiO2

To obtain a rapid, efficient synthesis of some new α-aminophosphonates, ultrasonic irradiation has been applied to the reaction mixtures containing amine, aromatic or heteroaromatic aldehydes and triethyl phosphite. The Kabachnik-Fields reaction was performed by using nano-BF₃?SiO₂ as a recyclable catalyst under solvent free conditions. Key advantages of this procedure consist in the eco-friendly and highly efficient reaction conditions, high yields, an easy work-up procedure, short reaction times and solvent free conditions. All title compounds were characterized by spectral and elemental analysis. They were further screened for their in vitro antioxidant activity by the DPPH, O^2? and NO methods. The majority of the title compounds showed good antioxidant activity when compared with the standard antioxidants.     

Studies of the Henry reaction catalyzed by Cu–O and Zn–O complexes with dimethoxysilane-bridged derivatives

Dimethyldimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane have been synthesized by a one-step, simple method and used as catalysts in the Henry reaction with Cu(OAc)₂·H₂O and Zn(OAc)₂·2H₂O, affording 60–96% conversion under the optimum catalytic conditions.     

Enantioselective α-chlorination of β-oxo esters catalyzed by chiral diterpenoid alkaloid derivatives

Easily accessible diterpenoid alkaloid derivatives have been used as organocatalysts in the enantioselective α-chlorination of β-oxo esters. The treatment of β-oxo esters with N-chlorophthalimide (NCP) as a chlorine source under mild reaction conditions afforded the corresponding α-chlorinated β-oxo esters in excellent yields (up to 98%) and with moderate enantioselectivities (up to 68% ee) in 30 min.     

Stereoselective synthesis of tetrahydropyran new derivatives underlain by α-allyl ketones

Decarboxylation of α-allyl-substituted acetoacetic esters afforded α-allyl ketones that were reduced with L-selectride [LiBH(s-Bu)₃] in alcohols RCH(OH)CH₂CH₂CH=C(Me)CH₂R'. The latter reacted with methyl 4-hydroxy-3-formylbenzoate and methyl orthoformate in the presence of p-toluenesulfonic acid to provide trans-tetrahydropyrano[3,2-с][1]benzopyran. In reaction of the E-isomer of alcohol Me₂CHCH(OH) CH₂CH₂CH=C(Me)CH₂CH₂Ph with CF₃SO₃H a stereoselective cyclization occurred with the formation of 2,6-disubstituted tetrahydropyran; Prins reaction with 4-bromobenzaldehyde and salicylaldehyde in the presence of boron trifluoride etherate also proceeded stereoselectively giving a substituted tetrahydropyrano-[3,2-c][1]-benzopyran.     

Iron-catalyzed decarbonylation reaction of aliphatic carboxylic acids leading to α-olefins

The catalytic decarbonylation reaction of aliphatic carboxylic acids can be carried out in the presence of an iron complex, and it proceeds smoothly to give α-olefins with high selectivity.     

Trimerization of aldehydes with one α-hydrogen catalyzed by sodium hydroxide

Trimerization of 2-methylpropanal (isobutyraldehyde) is a simple and effective method to synthesize 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate and 2,2,4-trimethyl-1,3-pentanediol-3-monoisobutyrate which are often used as film forming auxiliaries in paints. The use of solid sodium hydroxide as a catalyst provides an excellent yield of above 85 % after the optimization of the reaction time and the catalyst dosage. Furthermore, trimerization of four other aldehydes with one α-hydrogen catalyzed by solid sodium hydroxide can also take place and the yield of 1,3-diol monoesters reaches 50–70 %. Trimerization of aldehydes with one α-hydrogen can be explained by a three-step reaction mechanism: (i) aldol condensation of aldehyde; (ii) crossed Cannizzaro reaction; and (iii) esterification of carboxylic acid and alcohol.