79560-56-8

Upstream product

• 108-48-5 2,6-dimethylpyridine 
• 60-29-7 diethyl ether 
• 100-44-7 benzyl chloride 
• 591-51-5 phenyllithium 
• 931-19-1 2-methylpyridine N-oxide 
• 109-06-8 α-picoline 
• 100-42-5 styrene 
• 3262-89-3 triphenylboroxine 
• 71172-56-0 2-(2-methoxyethyl)-6-methylpyridine 
• 60340-28-5 1-phenylhex-5-en-3-ol 
• 78-94-4 methyl vinyl ketone 

Downstream Products

• 79560-57-9 2-methyl-6-dibenzylmethyl pyridine 
• 68031-94-7 2,6-bis (2-phenylethyl) pyridine 

Relevant academic research and scientific papers

Addition of C-H Bonds of Pyridine Derivatives to Alkenes Catalyzed by Zirconium Complexes Bearing Amine-Bridged Bis(phenolato) Ligands

Cationic zirconium complexes in situ generated from zirconium dibenzyl complexes bearing amine-bridged bis(phenolato) ligands have been developed to catalyze addition of C(sp2)-H and C(sp3)-H bonds of pyridine derivatives to alkenes.

Ortho-C–H addition of 2-substituted pyridines with alkenes and imines enabled by mono(phosphinoamido)-rare earth complexes

We here reported a special catalytic performance of mono(phosphinoamido)-ligated rare earth complexes in ortho-C–H functionalization of pyridines with nonpolar alkenes and polar imines. Upon treatment with one equiv. of borate reagent B(C6F5)3 or [Ph3C][B(C6F5)4], complex NP1-Sc can act as an efficient catalyst for ortho-C–H alkylation of pyridines towards alkenes. In the presence of 1:1 mixed secondary amine of HN (SiMe3)2 and HNBn2, complex NP2-Gd can catalyze ortho-C–H addition of pyridines towards imines, effectively. A wide range of substrates were subjected to the catalysis to render the one step synthesis of a variety of ortho-alkylated and ortho-aminoalkylated pyridine derivatives in good yields and an excellent regioselectivity and chemoselectivity.

Tris(benzhydryl) and Cationic Bis(benzhydryl) Ln(III) Complexes: Exceptional Thermostability and Catalytic Activity in Olefin Hydroarylation and Hydrobenzylation with Substituted Pyridines

A series of Ln(III) tris(benzhydryl) complexes [(p-tBu-C6H4)2CH]3Ln (Ln=La (1), Nd (2), Y (3)) were synthesized by the salt metathesis reactions of LnHal3(THF)3.5 (Ln=La, Nd, Hal=Cl; Ln=Y, Hal=I) and [(p-tBu-C6H4)2CH]Na. In 1–3 the benzhydryl ligands are linked with the metal centres in η4-coordination mode. For diamagnetic complexes 1 and 3 a fluxional behaviour was detected in solution. Complexes 1–3 proved to be thermally stable: no decomposition was observed even after heating their solutions in toluene-d8 at 140 °C during 72 h. The reactions of 1 and 2 with B(C6F5)3 allowed for the synthesis of base-free cationic complexes [(p-tBu-C6H4)2CH]2Ln[(p-tBu-C6H4)2CHB(C6F5)3] (Ln=La (4), Nd (5)) which adopt the structure of a contact ion pair. Combinations of 1–3 and borane ((B(C6F5)3, [Me2NHPh][B(C6F5)4], [Ph3C][B(C6F5)4]) as well as 4 and 5 were found to be highly efficient, regio- and chemoselective catalysts for hydroarylation and hydrobenzylation of C=C bonds of a variety of substrates with substituted pyridines. These catalysts enable highly challenging transformations such as hydrobenzylation of 1,1-disubstituted and internal C=C bonds. (Figure presented.).

Regio- and Stereoselective Alkylation of Pyridine-N-oxides: Synthesis of Substituted Piperidines and Pyridines

Regio- and stereoselective addition of alkyl Grignard reagents to pyridine-N-oxides gave C2-alkylated N-hydroxy-1,2,5,6-tetrahydropyridines and trans-2,3-disubstituted N-hydroxy-1,2,5,6-tetrahydropyridines in good to excellent yields. These intermediates were aromatized or alternatively reduced in one-pot methodologies for efficient syntheses of alkylpyridines or piperidines, respectively. These reactions have a broad substrate scope and short reaction times.

Yttrium-catalyzed addition of benzylic C-H bonds of alkyl pyridines to olefins

Cationic half-sandwich yttrium alkyl complexes catalyze the ortho-selective benzylic C-H addition of dialkyl pyridines to various olefins, such as ethylene, 1-hexene, styrenes, and 1,3-conjugated dienes, to afford new alkylated and allylated pyridine derivatives (see scheme; Cp=C5Me 5). A cationic half-sandwich yttrium picolyl species, such as [CpY(2-CH2-6-CH3C5H3N)] +, has been confirmed to be a key active species in this transformation. Copyright

Ruthenium-catalyzed conversion of sp3 C-O bonds in ethers to C-C bonds using triarylboroxines

Catalytic conversion of unreactive sp3 C-O bonds in alkyl ethers to C-C bonds is described. Alkyl ethers bearing 2- or 4-pyridyl groups were coupled with triarylboroxines in the presence of a ruthenium catalyst. Triarylboroxines bearing a variety of functional groups including electron-withdrawing and -donating groups can be used for the reaction. No additional base was required for the coupling with the organoboron reagents, and base-sensitive groups can be tolerated. The reaction is considered to proceed via dehydroalkoxylation followed by addition of triarylboroxines to form C-C bonds.

Heteroaromatic synthesis via olefin cross-metathesis: Entry to polysubstituted pyridines

The olefin cross-metathesis reaction provides a rapid and efficient method for the synthesis of α,β-unsaturated 1,5-dicarbonyl derivatives which then serve as effective precursors to mono-tetrasubstituted pyridines. Manipulation of the key 1,5-dicarbonyl intermediate allows access to pyridines with a wide range of substitution patterns. An extension of this methodology facilitates the preparation of pyridines embedded within macrocycles, as exemplified by an efficient synthesis of (R)-(+)-muscopyridine. High levels of regiocontrol, short reaction sequences, and facile substituent variation are all notable aspects of this methodology.(Figure Presented)

PYRIDINES. PARTIE IX - PLURIBENZYLATION DE LA S-COLLIDINE ET DE LA LUTIDINE-2,6

A literature survey of the polymetalation of 2,6-lutidine 2 shows different results about the site(s) of deprotonation and condensation with various electrophiles.This discrepancy prompts us to examine the polylithiation (PhLi 3 equivalents, Et2O) of s-collidine 1, 2,6-lutidine 2 and more briefly of 2,4-lutidine 3.Polylithiation takes place exclusively at the methyl groups of the same position vs the ring nitrogen : 2- and/or 6-methyl of 1.The previous regioselectivity observed in the case of the monometalation in Et2O is maintained.From 1 and 2, polylithiation gives picolyl anions which lead by reaction with PhCH2Cl, simultaneously to mono-, di-symmetrical, di-non-symmetrical α-derivatives, and tri- and tetra-symmetrical α,α'-compounds; but no product is formed from a benzylic β-anion.In the same way, the deprotonation of 2-methyl-6-(2-phenylethyl) pyridine 17 leads to 2,6-bis (2-phenylethyl) pyridine 19 and 2-methyl-6-dibenzylmethyl pyridine 18, to the exclusion of the β-compound 2-methyl-6-(2,3-diphenylpropyl) pyridine 21.The latter compound is formed in low yield, besides 19 and 18, in the conditions of the Tchitchibabine reaction (NaNH2, toluene).The structure of the benzylated compounds was established mainly from the 1H-nmr data.No product was isolated which would result from the nucleophilic attack of the generated carbanions at the pyridine carbons.