52189-85-2

Upstream product

• 91460-43-4 ethyl-(1-methyl-2-phenyl-vinyl)-ether 
• 100-46-9 benzylamine 
• 103-79-7 1-phenyl-acetone 
• 673-32-5 1-Phenylprop-1-yne 
• 10147-11-2 propargyl benzene 

Downstream Products

• 130849-46-6 O,O-diethyl-1-N-benzylamino-1-methyl-2-phenyl-ethyl-phosphonate 
• 84139-39-9 O,O-diethyl-1-amino-1-methyl-2-phenyl-ethylphosphonate 
• 79014-66-7 1-amino-1-methyl-2-phenyl-ethylphosphonic acid 

Relevant academic research and scientific papers

An (Aminopyrimidinato)titanium catalyst for the hydroamination of alkynes and alkenes

A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive and easily accessible 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The hydroamination reactions of 1-phenylpropyne and terminal arylalkynes deliver the corresponding anti-Markovnikov addition products with excellent yields and regioselectivities. A new (aminopyrimidinato)titanium complex has been synthesised from inexpensive 2-(tert-butylamino)pyrimidine and [Ti(NMe 2)4] and used as a catalyst for the intermolecular hydroamination of alkynes as well as the cyclization of aminoalkenes. The complex represents the first example of a catalyst for the hydroamination of alkynes that contains an aminoheteroaromatic ancillary ligand.

A general study of aryloxo and alkoxo ligands in the titanium-catalyzed intermolecular hydroamination of terminal alkynes

A general study of the regioselective hydroamination of terminal alkynes in the presence of Ti(NEt2)4 and different aryloxo and alkoxo ligands is presented. Depending on the ligand the regioselectivity towards the Markovnikov and the anti-Markovnikov addition product can be controlled. The experimentally observed isomer distribution is explained perfectly by detailed theoretical investigations which demonstrate that the regioselectivity is determined by the relative stability of the corresponding alkynetitanium π complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Controlling selectivity: From Markovnikov to anti-Markovnikov hydroamination of alkynes

A remarkable control of regioselectivity is achieved for the titanium-catalyzed intermolecular hydroamination of various alkynes. Proper choice of the ligand enables a selectivity switch from the Markovnikov to the anti-Markovnikov products from M:anti-M = > 90:10 to >10:90. Depending on the catalyst a remarkable control of regioselectivity is achieved for the titanium-catalyzed intermolecular hydroamination of various alkynes. Proper choice of sterically hindered phenol ligands such as 1 and 4 enables a selectivity switch from the Markovnikov to the anti-Markovnikov products from M:anti-M = > 90:10 to > 10:90.

[Ind2TiMe2]: A general catalyst for the intermolecular hydroamination of alkynes

[Ind2TiMe2] (Ind=indenyl) is a highly active and general catalyst for the intermolecular hydroamination of alkynes. It catalyzes the reaction of primary aryl-, tert-alkyl-, sec-alkyl-, and nalkylamines with internal and terminal alkynes. In the case of unsymmetrically substituted 1-phenyl-2-alkylalkynes, the reactions occur with modest to excellent regioselectivities, whereby formation of the anti-Markovnikov regioisomers is favored. While the major product of hydroamination reactions of terminal arylalkynes is always the anti-Markovnikov isomer, alkylalkynes react with arylamines to preferably give the Markovnikov products. To achieve reasonable rates for the addition of sterically less hindered n-alkyland benzylamines to alkynes, these amines must be added slowly to the reaction mixtures. This behavior is explained by the fact that the catalytic cycle proposed on the basis of an initial kinetic investigation includes the possibility that the rate of the reaction increases with decreasing concentration of the employed amine. Furthermore, no dimerization of the catalytically active imido complex is observed in the hydroamination of 1-phenylpropyne with 4-methylaniline in the presence of [Ind2TiMe2] as catalyst. In general, a combination of [Ind2TiMe2]-catalyzed hydroamination of alkynes with subsequent reduction leads to the formation of secondary amines with good to excellent yields. Particularly impressive is that [Ind 2TiMe2] makes it possible for the first time to perform the reactions of n-alkyl- and benzylamines with 1-phenylpropyne in a highly regioselective fashion.

Cp*2TiMe2: An improved catalyst for the intermolecular addition of n-alkyl- and benzylamines to alkynes

Cp*2TiMe2 has been found to be a competent catalyst for the intermolecular addition of sterically less demanding n-alkyl- and benzylamines to internal alkynes. In the presence of 2.0-6.0 mol % of the catalyst, hydroamination reactions between n-propyl-, n-hexyl-, benzyl-, p-methoxybenzyl- or 2-phenylethylamine and diphenylacetylene, 3-hexyne or 4-octyne go to completion within 24 h or less at 114°C (oil bath temperature). After subsequent reduction of the initially formed imines with zinc-modified sodium cyanoborohydride in MeOH at 25°C, the corresponding secondary amines can be isolated in excellent yields (> 78%). Hydroamination/reduction sequences employing the unsymmetrically substituted alkyne 1-phenylpropyne give access to mixtures of regioisomeric secondary amines. The observed regioselectivity is low.

ORGANIC PHOSPHORUS COMPOUNDS 91. SYNTHESIS AND PROPERTIES OF 1-AMINO-2-ARYLETHYLPHOSPHONIC AND -PHOSPHINIC ACIDS AS WELL AS -PHOSPHINE OXIDES

The preparation, physical and spectroscopic properties of 1-amino-2-arylethylphosphonic, and -phosphinic acids as well as -phosphine oxides, the phosphorus analogues of phenylalanine are described, and the reactions of 1-amino-2-(4-fluorophenyl)ethylphosphonates with acetals, isocyanides, esters, acid anhydrides, activated aromatic nitro- and halogen compounds, and with N-protected alanine are reported.It is shown that several of the 1-amino-2-arylethylphosphonic acids are strong inhibitors of PAL and anthocyanin synthesis and also are quite active botryticides.Among the active compounds were 1-amino-2-(4-fluorophenyl)ethylphosphonic acid, 3f, and the methyl-substituted compounds 3k, 3l, and 3m.The fluoroderivative 3f was also effective as a seed-dressing agent in barley showing a 100percent protection against the fungus Fusarium nivale at 600 ppm.