109-05-7Relevant articles and documents
Production of Piperidine and δ-Lactam Chemicals from Biomass-Derived Triacetic Acid Lactone
Chen, Bingfeng,Xie, Zhenbing,Peng, Fangfang,Li, Shaopeng,Yang, Junjuan,Wu, Tianbin,Fan, Honglei,Zhang, Zhaofu,Hou, Minqiang,Li, Shumu,Liu, Huizhen,Han, Buxing
, (2021)
Piperidine and δ-Lactam chemicals have wide application, which are currently produced from fossil resource in industry. Production of this kind of chemicals from lignocellulosic biomass is of great importance, but is challenging and the reported routes gi
PIPERIDINE-MODIFIED FISCHER-TROPSCH SYNTHESIS
Kliger, G. A.,Lesik, O. A.,Mikaya, A. I.,Marchevskaya, E. V.,Zaikin, V. G.,et al.
, p. 435 - 438 (1991)
N-Alkylpiperidines with alkyl fragment length from C1 to C15 were synthesized by the reaction of CO + H2 + piperidine.The molecular mass distribution of the N-alkylpiperidines has two different distribution parameters α.Thus, α = 0.45 +/- 0.03 for C1-C5 alkyl fragments, while α = 0.65 +/- 0.02 for C6-C15.Piperidine was found to act as modifier reagent and chemical trap for the intermediates in the synthesis reaction.
Organolanthanide-catalyzed hydroamination. A kinetic, mechanistic, and diastereoselectivity study of the cyclization of N-unprotected amino olefins
Gagné, Michel R.,Stern, Charlotte L.,Marks, Tobin J.
, p. 275 - 294 (1992)
This contribution reports the efficient, regiospecific Cp'2LnR [Cp' = η5-Me5C5; R = H, CH(TMS)2,η3-C3H5, N(TMS)2; Ln = La, Nd, Sm, Y, Lu]-catalyzed hydroamination/cyclization of the amino olefins H2NCHR1R2CH=CH2 to yield the corresponding heterocycles HNCH(R1)R2CHCH3, where R1, R2, Nt (turnover frequency, h-1), °C: H, (CH2)2, 140, 60 °C; H, CMe2CH2, 95, 25 °C; H, (CH2)3, 5, 60 °C; CH3, (CH2)2, 45, 25 °C; H, CH(Me)CH2, 38, 25 °C; and o-C6H4, CH2, 13, 80 °C. In addition, Me2Si(Me4C5)2NdCH(TMS)2 effects the cyclization of CH3HN(CH2)3CH=CH2 and H2NCH2CMe2(CH2) 3CH=CH2 with Nt = 11 h-1 (25 °C) and 0.3 h-1 (60 °C), respectively. Reactions are zero-order in substrate over 3 or more half-lives, and for the cyclization of HvN(CH2)3CH=CH2 by catalyst precursor Cp'2LaCH(TMS)2, ΔH? = 12.7 (1.4) kcal mol-1 and ΔS? = -27 (5) eu. Kinetic isotope effects (kH/kD) of 2.7 (4) (60 °C), 5.2 (8) (25 °C), and 4.1 (8) (25 °C) are observed for the Cp'2LaCH(TMS)2-induced cyclizations of D2N(CH2)3CH=CH2, D2NCH(C-H3)(CH2)2CH=CH2, and D2NCH2C(CH3)2CH 2CH=CH2, respectively. Cyclization yields the corresponding DNCH-(R1)R2CHCH2D isotopomers exclusively. Cyclization of H2NCH2C(CH3)2CH 2CH=CH2 by catalyst precursor Cp'2LaCH(TMS)2 exhibits the solvent effect, ktoluene/kTHF = 5.3 (5). The complexes Cp'2LnNHR(H2NR) (Ln = La, R = CH3, CH2CH3; Ln = Nd, R = CH2CH3) and Cp'2LaNCH(CH3)CH2CR2CH 2(HNCH(CH3)CH2CR2CH2) (R = H, CH3) were synthesized to model species in the catalytic cycle. Crystallographic data for Cp'2LaNHCH3(H2NCH3) at -120 °C were as follows: P21, Z = 4, a = 19.901 (4) A?, b = 11.695 (3) A?, c = 20.202 (3) A, β- 97.95 (2)°, and R(F) = 0.049 for 3296 independent reflections with I > 2.58σ(I). Two independent molecules crystallize per unit cell with average La-NHCH3 and La←NH2CH3 bond distances of 2.31 (1) and 2.70 (1) A?, respectively. The two molecules differ slightly in relative orientations of the NCH2 groups. The amine-amido complexes undergo rapid intramolecular proton transfer between amine and amido ligands (Δ? ≈ 12.4 ± 0.5 kcal mol-1). Intermolecular exchange with free amine is rapid on the NMR time scale at -80 °C. The ordering of precatalyst activities, (Cp'2LaCH(TMS)2 > Cp'2mCH(TMS)2 > Cp'2LuCH(TMS)2; Et2Si(C5H4)-(Me4C 5)LuCH(TMS)2 > Me2Si(Me4C5)2LuCH(TMS)2 > Cp'2LuCH(TMS)2) accords with known olefin insertion reactivities. Diastereoselection in H2NCH(CH3)(CH2)2CH=CH2 (5) cyclization depends on both lanthanide and ancillary ligation. Final 2,5-dimethylpyrrolidine transtcis ratios in LnLnR-catalyzed reactions for Ln, Ln, trans:cis, °C are as follows: Cp'2, La, 3:2, 50 °C; Cp'2, La, 5:1, 25 °C; Cp'2, La, 8:1, 0 °C; Cp'2, Nd, 1:1.25, 25 °C; Cp'2, Sm, 1:1.25, 25 °C; Cp'2, Y, 8:1, 25 °C; Me2Si(Me4C5)2, Y, 3:1, 25 °C; Et2Si(H4C5)(Me4C5), Y, 18:1, 25 °C; Et2Si(H4C5)(Me4C5), Lu, 4:1, 25 °C. For the Cp'2LaCH(TMS)2-catalyzed case, the trans:cis ratio is also dependent on the extent of conversion and initial substrate:catalyst ratio. In contrast to 5, 5d2 exhibits low diastereoselectivity which is independent of conversion. In the presence of 3 equiv of n-propylamine, the Cp'2LaCH(TMS)2-catalyzed cyclization of 5 affords a ≥50:1 trans:cis product ratio. Mechanistic evidence suggests that olefin insertion into the Ln-N bond of the amine-amido complexes is turnover-limiting and is followed by a rapid protonolysis of the resulting Ln-C bond. The proposed catalytic mechanism invokes parallel manifolds, with one manifold populated at high amine concentrations exhibiting high diastereoselectivity in the cyclization of 5, and with the second, favored at low substrate concentrations, exhibiting lower diastereoselectivity. The catalyst at high amine concentrations is postulated to be a Ln(amido)(amine)2 complex.
Lysinol: A renewably resourced alternative to petrochemical polyamines and aminoalcohols
Metkar, Pranit S.,Scialdone, Mark A.,Moloy, Kenneth G.
, p. 4575 - 4586 (2014)
This paper reports the preparation of lysinol (2,6-diamino-1-hexanol) by the hydrogenation of lysine and an example of its use as a replacement for petrochemical-derived amines. Lysine is presently manufactured by fermentation of sugars and other carbon sources at scale exceeding 109 kg per year. Therefore, lysinol is potentially a renewable, platform aminoalcohol of previously unrecognized potential. Lysine hydrogenation proceeds under relatively modest conditions with Ru/C catalyst in water (100-150 °C, 48-70 bar, pH 1.5-2) to give lysinol in good yield (100% conversion, >90% selectivity; 50-70% isolated yield after purification by distillation). The impact of the various reaction parameters on conversion and selectivity are presented and discussed. Lysine hydrogenation at higher temperatures provides a pathway to piperidines and other products via further reduction and elimination of lysinol. The feasibility of lysinol synthesis from commodity, animal feed-grade lysine sources is presented as well. An example of the potential utility of lysinol is demonstrated by its use as a diamine curing agent with a standard epoxy resin. The properties of the resulting thermoset are contrasted with that obtained with a typical petrochemical amine used in this application (diethylenetriamine, DETA). This journal is
Rigid NON-donor pincer ligand complexes of lutetium and lanthanum: Synthesis and hydroamination catalysis
Motolko, Kelly S. A.,Emslie, David J. H.,Britten, James F.
, p. 27938 - 27945 (2017)
Reaction of H2XN2 {4,5-bis(2,4,6-triisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene} with [Lu(CH2SiMe3)3(THF)2], and crystallization from O(SiMe3)2, yielded [(XN2)Lu(CH2SiMe3)(THF)]·(O(SiMe3)2)1.5 (1·(O(SiMe3)2)1.5). Lanthanum complexes of the XN2 dianion were also prepared by salt metathesis; treatment of H2XN2 with excess KH in DME produced the dipotassium salt, [K2(XN2)(DME)x] (x = 2-2.5), and subsequent reaction with [LaCl3(THF)3] afforded [{(XN2)LaCl(THF)}x]·(O(SiMe3)2)0.25x (2·(O(SiMe3)2)0.25x; x = 1 or 2) after crystallization from O(SiMe3)2. Compound 2 reacted with two equivalents of LiCH2SiMe3, to form the dialkyl-'ate' complex, [Li(THF)x][(XN2)La(CH2SiMe3)2]·Toluene·LiCl (3·toluene·LiCl; x = 3). Both 1 and 3 (x = 4) were structurally characterized, and were evaluated as catalysts for intramolecular hydroamination; while 3 showed poor activity, 1 is highly active for both intramolecular hydroamination and more challenging intermolecular hydroamination. Reactions with unsymmetrical alkenes yielded Markovnikov products, and the activity of 1 surpassed that of the previously reported yttrium analogue in the reaction of diphenylacetylene with 4-tert-butylbenzylamine.
Group 4 Complexes Bearing Pyrrolide Ligand for Intramolecular Alkene Hydroamination and Activation of C≡N Bond
Jiang, Zhilei,Wang, Yalan,Liu, Wei,Li, Yahong
, p. 844 - 848 (2018)
Titanium and zirconium complexes supported by a pyrrolide ligand HL1 [HL1 = 2-cyano-1H-pyrrole], Ti2(L2)2(NMe2)2 (1) and Zr3(L2)3(NMe2)6 (2) [L2 = N,N-dimethyl-1H-pyrrol-2-carboximidamide, NMe2-L1] were synthesized and characterized. The ligand L2 was generated by activation of C≡N bond of HL1 with HNMe2. In complex 1, two TiIV atoms are bridged by two nitrogen atoms. There are three characteristic ZrIV ions in 2, which are six-, seven- and six-coordinate, respectively. They were tested as catalysts for the intramolecular hydroamination of aminoalkenes, and the respective N-heterocycles were afforded in 74–99 % yields. Moreover, the formation of L2 ligand indicates that the amination of C≡N bond can be considered as a new and rapid way to synthesize other C–N bonds.
Yttrium and Aluminum Alkyl Complexes of a Rigid Bis-Anilido NON-Donor Ligand: Synthesis and Hydroamination Catalysis
Motolko, Kelly S. A.,Emslie, David J. H.,Jenkins, Hilary A.
, p. 1601 - 1608 (2017)
The palladium-catalyzed coupling of 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene (XBr2) with 2 equiv of 2,4,6-triisopropylaniline afforded the proligand 4,5-bis(2,4,6-triisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene (H2XN2), and reaction of H2XN2 with [Y(CH2SiMe2R)3(THF)2] (R = Me, Ph) produced the monoalkyl yttrium complexes [(XN2)Y(CH2SiMe2R)(THF)] (R = Me (1a), Ph (1b)). Neutral 1a showed near-zero ethylene polymerization activity (1 atm, 20 and 80 °C), and in the presence of AlMe3, 1a converted to [(XN2)Y{(μ-Me)2AlMe2}(THF)] (2). Compound 2 is thermally robust, and transfer of the XN2 ligand from yttrium to aluminum was not observed even at elevated temperatures. However, [(XN2)AlMe] (3) was accessible via the reaction of H2XN2 with AlMe3, demonstrating the ability of the wide-bite-angle XN2 ligand to coordinate to much smaller aluminum(III). Neutral 1a proved to be highly active for both intra- and intermolecular hydroamination with various substrates, yielding Markovnikov products in the intermolecular hydroamination reactions with 1-octene.
On the role of β hydrogen atoms in the hydrodenitrogenation of 2-methylpyridine and 2-methylpiperidine
Prins,Egorova,Zhao,Kukula
, p. 263 - 271 (2002)
Heterocyclic compounds like pyridine, quinoline, and acridine are the main nitrogen-containing compounds in oil. They are removed by HDN in a hydrotreating process in which gasoline or gas oil is treated with hydrogen over a metal sulfide catalyst. The HD
Facile Reduction of Pyridines with Nickel-Aluminum Alloy
Lunn, George,Sansone, Eric B.
, p. 513 - 517 (1986)
Nickel-aluminum alloy in dilute base can be used to reduce a variety of pyridines, quinolines, and isoquinoline to the corresponding piperidines, 1,2,3,4-tetrahydroquinolines, and 1,2,3,4-tetrahydroisoquinoline in good yield.The reaction is simple to perform, and high temperatures, high pressures, or hydrogen atmospheres are not required.The reaction is accelerated by substituents in the 2-position and by electron-withdrawing groups in the 3- and 4-positions while electron-supplying groups in the 3- and 4-positions retard the reaction.The major product isolated from the reduction of 2-phenylpyridine was 2-cyclohexylpiperidine hydrochloride.With isoniazid (1) and iproniazid (4) the pyridine ring is hydrogenated before the hydrazine is cleaved.
Characterization of three novel enzymes with imine reductase activity
Gand,Müller,Wardenga,H?hne
, p. 126 - 132 (2014)
Imine reductases (IRED) are promising catalysts for the synthesis of optically pure secondary cyclic amines. Three novel IREDs from Paenibacillus elgii B69, Streptomyces ipomoeae 91-03 and Pseudomonas putida KT2440 were identified by amino acid or structural similarity search, cloned and recombinantly expressed in E. coli and their substrate scope was investigated. Besides the acceptance of cyclic amines, also acyclic amines could be identified as substrates for all IREDs. For the IRED from P. putida, a crystal structure (PDB-code 3L6D) is available in the database, but the function of the protein was not investigated so far. This enzyme showed the highest apparent E-value of approximately Eapp = 52 for (R)-methylpyrrolidine of the IREDs investigated in this study. Thus, an excellent enantiomeric purity of >99% and 97% conversion was reached in a biocatalytic reaction using resting cells after 24 h. Interestingly, a histidine residue could be confirmed as a catalytic residue by mutagenesis, but the residue is placed one turn aside compared to the formally known position of the catalytic Asp187 of Streptomyces kanamyceticus IRED.
