58288-30-5Relevant academic research and scientific papers
Enantioselective Synthesis of α-Aryl-β2-Amino-Esters by Cooperative Isothiourea and Br?nsted Acid Catalysis
Zhao, Feng,Shu, Chang,Young, Claire M.,Carpenter-Warren, Cameron,Slawin, Alexandra M. Z.,Smith, Andrew D.
supporting information, p. 11892 - 11900 (2021/04/28)
The synthesis of α-aryl-β2-amino esters through enantioselective aminomethylation of an arylacetic acid ester in high yields and enantioselectivity via cooperative isothiourea and Br?nsted acid catalysis is demonstrated. The scope and limitatio
A General Acid-Mediated Hydroaminomethylation of Unactivated Alkenes and Alkynes
Kaiser, Daniel,Tona, Veronica,Gon?alves, Carlos R.,Shaaban, Saad,Oppedisano, Alberto,Maulide, Nuno
supporting information, p. 14639 - 14643 (2019/09/17)
In comparison to the extensively studied metal-catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State-of-the-art protocols for hydroaminomethylation of alkenes rely largely on transition-metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid-mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench-stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported.
Tuning the inclusion properties and solid-state reactivity of second sphere adducts using conformationally flexible bidentate ligands
Guo, Fang,Wang, Xu,Guan, Hong-Yu,Yu, Hai-Bin,Li, Lei,Chen, Shan-Shan,Famulari, Antonino,Martí-Rujas, Javier
, p. 2842 - 2852 (2015/06/16)
Second-sphere coordination refers to any intermolecular interaction with the ligands directly bound to the primary coordination sphere of a metal ion. In this article, we have successfully applied the second-sphere coordination approach in the construction of versatile host frameworks that can accommodate various guest molecules. We have used a family of bidentate flexible molecules as second-sphere ligands, and the tetrachlorometalate anion [MCl4]2- (where M = Cu, Co, Cd, Zn, and Hg) as the primary coordination sphere to synthesize new second sphere adducts. By introducing an alkyl spacer -(CH2)n- (n = 1, 2, 3, 4) to bibenzylamine (L0), the ligands L1, L2, L3, and L4 with higher degree of flexibility were synthesized. Different guest molecules such as alcohol, acetic acid, acrylic ester, or acetonitrile can be included in the host framework self-assembling diprotonated L1-L4 and [MCl4]2-, leading to a novel type of supramolecular assemblies: CH3CH2OH[L2]2H+·[CuCl4]2- (2), CH3OH[L3]2H+·[MCl4]2- (3), CH3COOH[L3]2H+·[CuCl4]2- (4), CH2CHCOOCH3'[L3]2H+·[MCl4]2- (5-7), CH3CN·H2O'[L4]2H+·[MCl4]2- (8-9), and CH3OH'[L4]2H+·[MCl4]2- (10). L2 forms the quasi-chelating charge-assisted N-H···Cl hydrogen bonds with [MCl4]2- that can transform in the solid-state to a chelated coordination complex following a mechanochemical dehydrochlorination reaction. By increasing the number of methylene groups, ligands L3 and L4 exhibit considerable conformational diversity due to the higher flexibility induced by the backbone chains. The -(CH2)n- spacer lengths of the ligands influences the structural dimensionality, and its solid-state mechanochemical reactivity preventing the transformation from salt [L3-4]2H+·[MCl4]2- to the chelating coordination complex [(MCl2)(L3-4)]. Moreover, the thermal stability of the second sphere adducts has been monitored by thermogravimetric analyses and X-ray powder diffraction (PXRD). We demonstrate that some of the second sphere adducts are dynamic, showing reversible guest release/uptake involving crystalline-to-amorphous-to-crystalline phase transformations. QuantumMechanical (QM) demonstrate that ligands with backbone lengths longer than -(CH2)2- are reticent to react via dehydrochlorination reaction because of the backbone chain length, the symmetry and orientation of the frontier molecular orbitals (FMOs), while for the -(CH2)2-, the length and orientation of the FMOs is optimal for the reaction to occur.
Ynamide Carbopalladation: A Flexible Route to Mono-, Bi- and Tricyclic Azacycles
Campbell, Craig D.,Greenaway, Rebecca L.,Holton, Oliver T.,Walker, P. Ross,Chapman, Helen A.,Russell, C. Adam,Carr, Greg,Thomson, Amber L.,Anderson, Edward A.
supporting information, p. 12627 - 12639 (2015/09/01)
Bromoenynamides represent precursors to a diversity of azacycles by a cascade sequence of carbopalladation followed by cross-coupling/electrocyclization, or reduction processes. Full details of our investigations into intramolecular ynamide carbopalladation are disclosed, which include the first examples of carbopalladation/cross-coupling reactions using potassium organotrifluoroborate salts; and an understanding of factors influencing the success of these processes, including ring size, and the nature of the coupling partner. Additional mechanistic observations are reported, such as the isolation of triene intermediates for electrocyclization. A variety of hetero-Diels-Alder reactions using the product heterocycles are also described, which provide insight into Diels-Alder regioselectivity.
Dibenzylammonium hydrogen maleate and a redetermination at 120K of bis(dibenzylamino)methane
Castillo, Juan C.,Abonia, Rodrigo,Cobo, Justo,Glidewell, Christopher
, p. 798 - 802 (2013/07/26)
In dibenzylammonium hydrogen maleate [or dibenzylammonium (2Z)-3-carboxyprop-2-enoate], C14H16N+· C4H3O4 -, (I), the anion contains a fairly short and nearly linear O - H...O hyd
New scalable asymmetric aminomethylation reaction for the synthesis of β2-amino acids
Moumne, Roba,Denise, Bernard,Guitot, Karine,Rudler, Henri,Lavielle, Solange,Karoyan, Philippe
, p. 1912 - 1920 (2008/02/06)
β-Amino acids are useful tools in the design of peptidomimetics, and the development of new methods for their syntheses, particularly the synthesis of β2-amino acids, remains an important challenge. Here we report a new scalable route based on the aminomethylation of silyl ketene N,O-acetals by Mannich-type iminium electrophiles. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Aminomethylation of functionalized organozinc reagents and grignard reagents using immonium trifluoroacetates
Millot, Nicolas,Piazza, Claudia,Avolio, Salvatore,Knochel, Paul
, p. 941 - 948 (2007/10/03)
New immonium trifluoroacetates 1 and 2 react readily with functionalized organozinc or magnesium reagents leading to the corresponding aminomethylated products of type 5 and 7. The resulting bis-allylamines were deallylated leading to primary amines.
