4541-69-9

Upstream product

• 1117-96-0 Diazoethan 
• 5873-86-9 methyl thiobenzoate 
• 14222-20-9 1R,2R-N-methylpseudoephedrine 
• 74-88-4 methyl iodide 
• 67-56-1 methanol 
• 321-97-1 (1R,2R)-pseudoephedrine 
• 93-55-0 1-phenyl-propan-1-one 
• 149-73-5 trimethyl orthoformate 
• 102654-45-5 2-bromo-1-methoxy-1-phenylpropane 
• 124-41-4 sodium methylate 
• 93-58-3 benzoic acid methyl ester 
• 557-91-5 1,1-Dibromoethane 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 98-86-2 acetophenone 

Downstream Products

• 65501-11-3 1-azido-1-phenylethyl methyl ether 
• 74209-87-3 threo-3-methoxy-2-methyl-1,3-diphenylpropan-1-one 
• 74209-87-3 erythro-3-methoxy-2-methyl-1,3-diphenylpropan-1-one 
• 5650-40-8 (S)-2-hydroxypropiophenone 
• 5650-40-8 (R)-2-hydroxy-1-phenylpropan-1-one 
• 93-58-3 benzoic acid methyl ester 
• 4165-86-0 (E)-(1-ethylpropenyl)benzene 
• 51181-43-2 3,4-Dimethyl-2,5-diphenylfuran 
• 93-55-0 1-phenyl-propan-1-one 
• 4013-34-7 3-phenyl-2-oxabutane 
• 1196450-32-4 1-tert-butyldiphenylsiloxy-5-methoxy-4-methyl-5-phenylcyclopent-1-ene 
• 14255-25-5 4-phenyl-1,4-hexadiene 
• 1009-81-0 1,5-hexadien-1-yl-benzene 
• 87456-64-2 α-tosyloxypropiophenone 

Relevant academic research and scientific papers

Preparation of alkylated compounds using the trialkylphosphate

[Problem] trialkylphosphate strong base used reaction agent, a carboxylic acid, a ketone, an aldehyde, amine, amide, thiol, ester or Grignard reagent to a variety of substrates, and/or high efficiency to generate a highly stereoselective alkylation reaction, the alkylated compounds capable of producing new means. [Solution] was used as the alkylating agent in the alkylation of compound trialkylphosphate, strongly basic reaction production use. [Drawing] no

Regio- And Stereoselective (S N2) N -, O -, C - And S -Alkylation Using Trialkyl Phosphates

Bimolecular nucleophilic substitution (S N 2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N -, O -, C - and S -nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).

A step forward in solvent knitting strategies: Ruthenium and gold phosphine complex polymerization results in effective heterogenized catalysts

Porous polymers based on ruthenium and gold triphenylphosphine complexes (KPhos(Ru), KPhos(Ru)Bi, KPhos(AuCl) and KPhos(AuNTf2)) were prepared via a cost-effective solvent knitting method with [RuHClCO(PPh3)3] or AuXPPh3 (X = Cl, NTf2) as single monomers or combined with biphenyl, which represents a further approach to obtain heterogenized catalysts. The resulting materials mainly preserve the metal coordination environment of their parent complexes, are stable up to 350 °C and have reasonable surface areas (250-300 m2 g-1 for KPhos(Ru)-polymers). KPhos(Ru)s selectively catalyze the imination of alcohols in the presence of base and the results for KPhos(Au)s show they are effective for the intermolecular hydration and hydroamination of alkynes. These materials can be reused several times without significant loss of activity. This novel and simple method affords heterogenized catalysts that combine the reactivity and selectivity of their homogeneous counterparts with the stability and reusability of a heterogeneous framework.

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3.

Study of the Reactivity of [Hydroxy(tosyloxy)iodo]benzene Toward Enol Esters to Access α-Tosyloxy Ketones

The reactivity of enol esters toward [hydroxy(tosyloxy)iodo]benzene (HTIB) was assessed. These substrates were found to be rapidly converted in high yields to their corresponding α-tosyloxy ketones. This transformation demonstrates that these substrates can act as ketone surrogates. The scope of the method was investigated and aromatic, aliphatic, and cyclic enol esters were found to be suitable substrates for the reaction. The relative reactivity of a model substrate toward HTIB and m-CPBA was investigated, and it was found that the reaction could be performed under catalytic conditions.

Thermal and photochemical solvolysis of (E)- and (Z)-2-phenyl-1-propenyl(phenyl)iodonium tetrafluoroborate: Benzenium and primary vinylic cation intermediates

The thermal and photochemical solvolysis of the two stereoisomeric 2-phenyl-1-propenyl(phenyl)-iodonium tetrafluoroborates has been investigated in alcoholic solvents of varying nucleophilicity. The product profiles and rates of product formation in the thermal reaction are all compatible with a mechanism involving cleavage of the vinylic C - I bond assisted by the group in the trans position (methyl or phenyl), always leading to rearranged products. Depending on the nucleophilicity of the solvent, the primarily formed cations may or may not further rearrange to more stable isomers. The less reactive Z compound also yields some unrearranged vinyl ether product in the more nucleophilic solvents via an in-plane SN2 mechanism. The mechanism of the photolysis involves direct, unassisted cleavage of the vinylic, and aromatic, C - I bond in an SN1 mechanism. This produces a primary vinyl cation, which is partially trapped prior to rearrangement in methanol. The unrearranged vinyl ethers are mainly formed with retention of configuration via a λ3-iodonium/solvent complex in an SNi mechanism. Thermal and photochemical solvolyses of iodonium salts are complementary techniques for the generation of different cation intermediates from the same substrate.

TRICARBONYLCHROMIUM(0) PROMOTED STEREOSELECTIVE TRANSFORMATIONS OF EPHEDRINE AND PSEUDOEPHEDRINE DERIVATIVES

(-)-(1S,2S)-(N,O-Dimethylephedrine)tricarbonylchromium(0) (6) and (-)-(1S,2R)-(N,O-dimethylpseudoephedrine)tricarbonylchromium(0) (22) undergo completely stereoselective ortho deprotonation upon treatment with alkyllithium base, followed by addition of an electrophile.In both cases, exclusive remolval of the pro-(R)-ortho proton was confirmed by single X-ray structure analyses of the methylated products.Addition of methyllithium onto the ortho-formylated derivative of complex (6) occurs stereoselectively, the stereochemistry of the major product being confirmed by a single crystal X-ray structure determination.The results presented demonstrate an efficient transfer of chirality from a side chain onto the (arene)tricarbonylchromium(0) complex and back to a different side chain.

Influence of Solvent and Cation on the Properties of Oxygen-containing Organic Anions. Part 1. Regioselectivity of Methylation of Acetophenone Enolate

Acetophenone enolates of lithium, sodium, and potassium were methylated with dimethyl sulphate in 14 aprotic solvents.Linear correlations of the logarithm of the molar ratio of O-methylation versus C-methylation products log(QO/QC) with solvent polarity and Lewis basicity parameters and either the ionic radius rM or the reciprocal of the ionic volume (rM-3) of the metal were found.The results were interpreted with the help of HOMO energies of the enolates, their polarity index qO/qC (excess of negative charge densities on O and α-C), and frontier orbital index cC2/cO2, as a function of the correcting parameter δO in HMO calculations which characterizes the action of the cation field upon the electron distribution in the enolate.

Alkylidenation of Ester Carbonyl Groups by means of a Reagent Derived from RCHBr2, Zn, TiCl4, and TMEDA. Stereoselective Preparation of (Z)-Alkenyl Ethers

Reagents prepared by reduction of 1,1-dibromoalkanes (R3CHBr2) with zinc and TiCl4 in the presence of N,N,N',N'-tetramethylethylenediamine in THF are effective in the conversion of esters (R1CO2R2) to the corresponding alkenyl ethers (R1(R2O)C=CHR3) with high Z selectivity.

New Methods and Reagents in Organic Synthesis. 34. Diphenyl Phosphorazidate (DPPA) as a 1,3-Dipole. A Simple, Efficient Conversion of Alkyl Phenyl Ketones to 2-Phenylalkanoic Acids

Propiophenone (11) was conveniently converted to its enamines 12a-c using boron trifluoride etherate as a catalyst.Reaction of diphenyl phosphorazidate (DPPA) with the enamines 12a-c efficiently afforded the N-phosphorylated amidines 14a-c by the 1,3-dipolar cycloaddition of DPPA to the enamine double bond, followed by the evolution of nitrogen from the intermediate triazoline 13, and 1,2-migration of the phenyl group. 1,3-Dipolar elimination products 15a-c were also formed, though in very low yields.Some chemical properties of the N-phosphorylated amidine 14a, as well as the 1,3-dipolar character of DPPA, were investigated.By the same reaction sequences (enamine formation followed by the 1,3-dipolar cycloaddition of DPPA), some alkyl phenyl ketones 29a-c were conveniently converted to the N-phosphorylated amidines 31a, 31b, and 27 via the enamines 30a-c.However , in the case of acetophenone and its derivatives 33a-c, these reaction sequences proceeded sluggishly.Alkaline hydrolysis of the N-phosphorylated amidines 14a, 31a, 31b and 27 with potassium hydroxide afforded 2-phenylalkanoic acids 25 and 32a-c, respectively, in excellent yields.The overall three-step process of successive treatment of alkyl phenyl ketones (alkylmethyl) with pyrrolidine, DPPA, and potassium hydroxide may provide a new general method for the efficient conversion of alkyl aryl ketones to 2-arylalkanoic acids.Keywords - enamine; diphenyl phosphorazidate; boron trifluoride etherate; 1,3-dipolar cycloaddition; 1,2-migration; N-phosphorylated amidine; alkaline hydrolysis; alkyl aryl ketone; 2-arylalkanoic acid