109925-99-7

Upstream product

• 19679-59-5 propiophenone N,N-dimethylhydrazone 
• 110775-25-2 3-phenylhept-6-en-2-one trimethylhdrazonium iodide 
• 109925-98-6 6-(Trimethylsilyl)methyl-3-phenyl-5,6-dihydro-4H-1,2-oxazine 
• 905445-07-0 3-phenyloct-7-en-2-one trimethylhdrazonium iodide 
• 98-86-2 acetophenone 
• 3240-29-7 1-Phenylpent-4-en-1-one 
• 592-51-8 4-Pentenenitrile 
• 108-86-1 bromobenzene 
• 98-88-4 benzoyl chloride 
• 21572-32-7 2-chloro-1-phenyl-ethanone oxime 
• 7103-09-5 4-but-1-enylmagnesium bromide 
• 100-47-0 benzonitrile 
• 100-58-3 phenylmagnesium bromide 
• 1334324-94-5 C₁₁H₁₃N₃ 

Downstream Products

• 342422-63-3 3-methyl-6phenyl-2-piperidinone 
• 1357391-22-0 trans-2-methyl-5-phenylpyrrolidine 
• 861882-42-0 (1-phenylpent-4-enyl)carbamic acid tert-butyl ester 
• 861882-43-1 N-(1-phenylpent-4-enyl)-acetamide 
• 1357391-22-0 trans-1-phenyl-4-methylpyrrolidine 
• 1357391-22-0 cis-2-Methyl-5-phenylpyrrolidine 
• 1357391-22-0 (2R,5S)-2-methyl-5-phenylpyrrolidine 
• 1357391-22-0 (2S,5R)-2-methyl-5-phenylpyrrolidine 
• 882883-57-0 (S)-(1-phenylpent-4-en-1-yl)amine 
• 928673-83-0 (R/S)-N-benzyloxycarbonyl-1-phenylpent-4-en-1-ylamine 

Relevant academic research and scientific papers

Palladium-catalyzed tandem N-arylation/carboamination reactions for the stereoselective synthesis of N-aryl-2-benzyl pyrrolidines

(Chemical Equation Presented) The tandem N-arylation/carboamination of γ-amino alkenes with two different aryl bromides provides rapid entry to differentially arylated N-aryl-2-benzyl pyrrolidine derivatives in good yields with good to excellent levels of diastereoselectivity. The selective diarylation is achieved in a one-pot process by an in situ modification of the palladium catalyst via phosphine ligand exchange.

Pd(II)-catalyzed allylic C-H amination for the preparation of 1,2- and 1,3-cyclic ureas

A general synthesis of 1,2- and 1,3-cyclic ureas is accomplished by intramolecular allylic C-H amination employing Pd(TFA)2/bis-sulfoxide as a catalyst. By careful modification of substrates and catalyst, a variety of 1,2-cyclic ureas are accessible from not previously employed terminal olefins substituted in allylic or vinylic positions. Furthermore, MS4A is found to be an effective additive for the synthesis of 1,3-cyclic ureas in good yields and excellent diastereoselectivities.

Pd(0)-catalyzed alkene oxy- and aminoalkynylation with aliphatic bromoacetylenes

Tetrahydrofurans and pyrrolidines are among the most important heterocycles found in bioactive compounds. Cyclization-functionalization domino reactions of alcohols or amines onto olefins constitute one of the most efficient methods to access them. In this context, oxy- and aminoalkynylation are especially important reactions, because of the numerous transformations possible with the triple bond of acetylenes, yet these methods have been limited to the use of silyl protected acetylenes. Herein, we report the first palladium-catalyzed oxy- and aminoalkynylation using aliphatic bromoalkynes, which proceeded with high diastereoselectivity and functional group tolerance. A one-pot hydrogenation of the triple bond gave then access to alkyl-substituted tetrahydrofurans and pyrroldines. Finally, a detailed study of the side products formed during the reaction gave a first insight into the reaction mechanism.

Pd(0)-catalyzed oxy- and aminoalkynylation of olefins for the synthesis of tetrahydrofurans and pyrrolidines

The first Pd(0)-catalyzed intramolecular oxy- and aminoalkynylation of nonactivated olefins is reported. The reaction gives access to important tetrahydrofuran and pyrrolidine heterocycles with high diastereoselectivity. The unique synthetic potential of acetylenes is further exploited to access key building blocks for the synthesis of bioactive natural products.

Diastereoselective control of intramolecular aza-Michael reactions using achiral catalysts

An intramolecular aza-Michael reaction with a Cbz carbamate and an enone is reported to result in 3,5-disubstituted nitrogen-containing heterocycles. Either cis or trans isomers were obtained selectively using chiral substrates and an achiral Pd (II) comp

Homogeneous gold-catalyzed oxidative carboheterofunctionalization of alkenes

(Chemical Equation Presented) Homogeneous carboamination, carboalkoxylation and carbolactonization of terminal alkenes are realized via oxidative gold catalysis, providing expedient access to various substituted Nor O-heterocycles. Deuterium-labeling studies established the anti nature of the alkene functionalization and the indispensible role of Au(I)/Au(III) catalysis. This study constitutes the first example of catalytically converting C(sp 3)-Au bonds into C(sp3)-C(sp2) bonds in a crosscoupling manner and opens new opportunities to study gold alkene catalysis where alkylgold intermediates can be readily functionalized intermolecularly. Copyright

Intramolecular hydroamination of aminoalkenes by calcium and magnesium complexes: A synthetic and mechanistic study

The β-diketiminate-stabilized calcium amide complex [{ArNC(Me)CHC(Me)NAr}Ca{N(SiMe3)2}-(THF)] (Ar = 2,6-diisopropylphenyl) and magnesium methyl complex [{ArNC(Me)CHC(Me)NAr}Mg(Me) (THF)] are reported as efficient precatalysts for hydroamination/cyclization of aminoalkenes. The reactions proceeded under mild conditions, allowing the synthesis of five-, six-, and seven-membered heterocyclic compounds. Qualitative assessment of these reactions revealed that the ease of catalytic turnover increases (i) for smaller ring sizes (5 > 6 > 7), (ii) substrates that benefit from favorable Thorpe-Ingold effects, and (iii) substrates that do not possess additional substitution on the alkene entity. Prochiral substrates may undergo diastereoselective hydroamination/cyclization depending upon the position of the existing stereocenter. Furthermore, a number of minor byproducts of these reactions, arising from competitive alkene isomerization reactions, were identified. A series of stoichiometric reactions between the precatalysts and primary amines provided an important model for catalyst initiation and suggested that these reactions are facile at room temperature, with the reaction of the calcium precatalyst with benzylamine proceeding with ΔG°(298 K) = -2.7 kcal mol-1. Both external amine/amide exchange and coordinated amine/amide exchange were observed in model complexes, and the data suggest that these processes occur via low-activation-energy pathways. As a result of the formation of potentially reactive byproducts such as hexamethyldisilazane, calcium-catalyst initiation is reversible, whereas for the magnesium precatalyst, this process is nonreversible. Further stoichiometric reactions of the two precatalysts with 1-amino-2,2-diphenyl-4-pentene demonstrated that the alkene insertion step proceeds via a highly reactive transient alkylmetal intermediate that readily reacts with N-H σ bonds under catalytically relevant conditions. The results of deuterium-labeling studies are consistent with the formation of a single transient alkyl complex for both the magnesium and calcium precatalysts. Kinetic analysis of the nonreversible magnesium system revealed that the reaction rate depends directly upon catalyst concentration and inversely upon substrate concentration, suggesting that substrate-inhibited alkene insertion is rate-determining.

3,3′-Bis(trisarylsilyl)-substituted binaphtholate rare earth metal catalysts for asymmetric hydroamination

Chiral 3,3′-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[Ln{Binol-SiAr3}(o-C6H 4CH2NMe2)(Me2NCH2Ph)] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3′-bis(trisarylsilyl)-2,2′- dihydroxy-1,1′-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[La{Binol-Si(3,5-xylyl)3}{E(SiMe3)2}(THF) 2] (E = CH (4a), N (4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, giving TOF of up to 840 h -1 at 25 °C for 2,2-diphenyl-pent-4-enylamine (5c) using (R)-2-Y. Enantioselectivities of up to 95% ee were achieved in the cyclization of 5c with (R)-2-Sc. The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, but rates depend on total amine concentrations. Activation parameters for the cyclization of pent-4-enylamine using (R)-2-Y (ΔH(S)? = 57.4-(0.8) kJ mol-1 and ΔS(S)? = -102(3) J K-1 mol-1; ΔH(R)? = 61.5(0.7) kJ mol-1 and ΔS(R)? = -103(3) J K-1 mol -1) indicate a highly organized transition state. The binaphtholate catalysts were also applied to the kinetic resolution of chiral α-substituted aminoalkenes with resolution factors f of up to 19. The 2,5-disubstituted aminopentenes were formed in 7:1 to ≥50:1 trans diastereoselectivity, depending on the size of the α-substituent of the aminoalkene. Rate studies with (S)-1-phenyl-pent-4-enylamine ((S)-15e) gave the activation parameters for the matching (ΔH? = 52.2(2.8) kJ mol -1, ΔS? = -127(8) J K-1 mol-1 using (S)-2-Y) and mismatching (ΔH? = 57.7(1.3) kJ mol -1, ΔS? = -126(4) J K-1 mol-1 using (R)-2-Y) substrate/catalyst combination. The absolute configuration of the Mosher amide of (2S)-2-methyl-4,4-diphenyl-pyrrolidine and (2R)-methyl-(5S)- phenyl-pyrrolidinium chloride, prepared from (S)-15e, were determined by crystallographic analysis. Catalyst (R)-4a showed activity in the anti-Markovnikov addition of n-propylamine to styrene.

Stereoselective synthesis of N-protected pyrrolidines via Pd-catalyzed reactions of γ-(N-acylamino) alkenes and γ-(N-Boc-amino) alkenes with aryl bromides

The stereoselective synthesis of N-acyl- and N-Boc-protected pyrrolidines via Pd-catalyzed reactions of γ-(N-acylamino) alkenes and γ-(N-Boc-amino) alkenes with aryl bromides is described. These reactions effect formation of two bonds in a single operation and proceed with generally high levels of diastereoselectivity. In contrast to previously described reactions of γ-(N-arylamino) alkenes, these transformations proceed in high yield and high regioselectivity with both electron-rich and electron-deficient aryl bromides as well as vinyl bromide substrates.

Kinetic resolution of chiral aminoalkenes via asymmetric hydroamination/cyclisation using binaplitholate yttrium complexes

Chiral binaphtholate yttrium aryl complexes are highly active and enantioselective catalysts for the asymmetric hydroamination of aminoalkenes, as well as the kinetic resolution of α-substituted 1-aminopent-4-enes to give trans-2,5-disubstituted pyrrolidines with good enantiomeric excess and high krel.