Rhodium-catalyzed addition of arylboron compounds to nitriles, ketones, and imines

The rhodium-catalyzed addition reactions of sodium tetraphenylborate and arylboronic acids to nitriles, ketones, and imines were examined. The reaction of nitriles could be carried out efficiently in the presence of a catalyst system of [RhCl(cod)]₂-dppp and H₂O to give the corresponding monoarylated products selectively. Although unactivated ketones and imines are known to be poor electrophiles for rhodium-catalyzed arylation, the phenylation of them with use of sodium tetraphenylborate proceeded smoothly in the presence of [RhCl(cod)]₂ and Rh(acac)(cod) as catalysts, respectively. The addition of NH₄Cl was found to be crucial to effectively conduct the reaction of ketones and imines.     

Chloride ion promoted nucleophilic pentafluorophenylation of imines

Nucleophilic addition of the pentafluorophenyl group from (C₆F₅)₃SiF to non-activated imines affording α-C₆F₅-substituted secondary amines in high yield has been described. The reaction proceeds via simultaneous activation of imines and the silane reagent by means of a proton and chloride ion, respectively.     

Magnesium perchlorate as an efficient catalyst for the synthesis of imines and phenylhydrazones

Magnesium perchlorate has been found to be an efficient catalyst for the synthesis of imines and phenylhydrazones by the reaction of carbonyl compounds with amines and phenylhydrazine in high yields at room temperatures and in short times. The condensation of less electrophilic carbonyl compounds with poorly nucleophilic amines affords the imines in excellent yields.     

Ruthenium-catalyzed cyclization of 3-en-1-ynyl imines with nucleophiles via tandem 5-exo-dig cyclization and nucleophilic addition

Treatment of 3-en-1-ynyl imines with TpRuPPh₃(CH₃CN)₂PF₆ catalyst (1 mol %) in DCE (50 °C, 6 h) effected catalytic cyclization with suitable nucleophiles and gave functionalized pyrroles in good yields. The reaction mechanism is proposed to proceed via (2-pyrrolyl)carbenoid intermediates derived from 5-exo-dig cyclization. This catalytic reaction works well with various nucleophiles, including water, alcohols and anilines.     

2‐Iminoimidazoline — starke Stickstoffbasen als Koordinationspartner in der Anorganischen Chemie

2‐Iminoimidazolines — Strong Nitrogen Bases als Ligands in Inorganic Chemistry Due to the tendency of the 5‐membered cyclic fragment to accept a positive charge which yields an ylide type bonding situation, 2‐iminoimidazolines are strong nitrogen bases. They can serve as neutral ligands being 2+2 electron donors. Deprotonation leads to the anions which are potential 2+4 electron donors. We describe first the synthesis and characterization of the title compound 2‐imino‐1, 3‐dimethylimidazoline (ImNH, 8 ) and its anion 9 . Next we demonstrate their properties as ligands in complexes of main group elements and transition metals. In a third chapter we describe attempts to functionalize iminoimidazolines with the goal to create neutral ligands that coordinate in a semistable fashion. On this way we want to make a contribution to the chemistry of complex compounds directed towards catalysis.     

A Convenient Synthesis of N‐Boc‐Protected α‐Aminonitriles from α‐Amidosulfones

Abstract

Synthesis of N‐Boc‐protected α‐aminonitriles starting from N‐Boc‐protected α‐aminosulfones is described. Treatment of the sulfone with two equivalents of potassium cyanide in 2‐propanol or dichloromethane‐H₂O under phase transfer condition affords crystalline N‐Boc‐protected α‐aminonitriles in good yield. Hydrolysis of the aminonitriles provides a convenient access to racemic α‐amino acids.     

Chiral bidiaziridines by a two-step domino aziridination of meso-α-diimines

Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO₂Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines.     

Sugar-derived cyclic imines: one-pot synthesis and direct functionalization

A simple method for the synthesis of sugar-derived imines by a Schwartz's reagent reduction of easily available sugar lactams has been described. A direct addition of nucleophiles to the generated in situ cyclic imines and subsequent deprotection of hydroxyl function allows to convert sugar lactams in polyhydroxylated pyrrolidines and piperidines.     

Synthesis of cis bis-β-lactams via Staudinger cycloaddition reaction using C2-symmetric 1,2-diamines

An efficient stereoselective synthesis of bis-β-lactams via cycloaddition reaction (Staudinger reaction) of ketenes with bisimines derived from C₂-symmetric 1, 2-diamines is described. The reaction provided diastereomeric mixture of meso and C₂-symmetric cis-bis-β-lactams with higher selectivity for meso-bis-β-lactams.     

Iron(II)‐ and Cobalt(II) Complexes with Tridentate Bis(imino)pyridine Nitrogen Ligands Bearing Chiral Bulky Aliphatic and Aromatic Substituents: Crystal Structure of [CoCl2{2, 6‐bis[R‐(+)‐(bornylimino)methyl]pyridine}]

Iron(II) and cobalt(II) complexes ( 7 ‐ 15 ) based on new aldimine 2, 6‐bis[(imino)methyl]pyridine ( 1 , 2 , 4 , 6 ) and ketimine (2, 6‐bis[(imino)ethyl]pyridine ( 3 , 5 ) ligands with bulky chiral aliphatic or aromatic terminal groups have been prepared and characterized by ¹H NMR, ¹³C NMR, IR‐, mass spectroscopy (EI), and elemental analysis. The complex [CoCl₂(BBoMP)]·¹/₂ CHCl₃ ( 13 ) (BBoMP: 2, 6‐bis{(R‐(+)‐(bornylimino)‐methyl}pyridine) crystallizes in monoclinic space group P2₁ with cell dimensions: a = 7.6603(11) Å, b = 28.3153(14) Å, c = 13.537(2) Å, V = 2908.1(6) ų, Z = 4. The coordination sphere around Co is distorted trigonal bipyramidal.