142186-19-4Relevant academic research and scientific papers
Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary
Buzzetti, Luca,Puri??, Mikus,Greenwood, Phillip D. G.,Waser, Jerome
, p. 17334 - 17339 (2020)
Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited in terms of either efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process.
“Backdoor Induction” of Chirality: Trans-1,2-cyclohexanediamine as Key Building Block for Asymmetric Hydrogenation Catalysts
Glasovac, Zoran,Kirin, Sre?ko I.,Kokan, Zoran,Opa?ak, Sa?a,Peri?, Berislav
, p. 2115 - 2128 (2019/01/04)
This paper describes the synthesis and characterization of 21 chiral monodentate ligands L, assembled of three building blocks utilizing amide bonds: a metal binding triphenylphosphine, a chiral cyclic diamine and an additional substituent for fine-tuning the steric and/or electronic properties. Cis square-planar metal complexes of RhI and PtII with ML2 stoichiometry have been prepared and characterized by spectroscopic methods (NMR, IR, UV-Vis, CD) and DFT calculations. A key feature of the metal complexes is a prochiral metal coordination sphere and “backdoor induction” of chirality from a distant chiral source via an outer-coordination sphere, well-defined by aromatic stacking and hydrogen-bonding. The rhodium complexes were used as catalysts in asymmetric hydrogenation of α,β-dehydroamino acids with excellent yield and selectivity (up to 97 % ee), strongly supporting the “backdoor induction” hypothesis.
Asymmetric conjugate addition of α,α-disubstituted aldehydes to nitroalkenes organocatalyzed by chiral monosalicylamides from trans-cyclohexane-1,2-Diamines
Martínez-Guillén, José R.,Flores-Ferrándiz, Jesús,Gómez, Cecilia,Gómez-Bengoa, Enrique,Chinchilla, Rafael
, (2018/01/18)
Primary amine-salicylamides derived from chiral trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to arylated and heteroarylated nitroalkenes. The reaction is performed in
Enantioselective michael addition of aldehydes to maleimides organocatalyzed by a chiral primary amine-salicylamide
Torregrosa-Chinillach, Alejandro,Moragues, Adrien,Pérez-Furundarena, Haritz,Chinchilla, Rafael,Gómez-Bengoa, Enrique,Guillena, Gabriela
, (2019/01/03)
A primary amine-salicylamide derived from chiral trans-cyclohexane-1,2-diamine was used as an organocatalyst for the enantioselective conjugate addition of aldehydes, mainly α,α-disubstituted to N-substituted maleimides. The reaction was performed in tolu
CDI-mediated monoacylation of symmetrical diamines and selective acylation of primary amines of unsymmetrical diamines
Verma, Sanjeev K.,Ghorpade, Ramarao,Pratap, Ajay,Kaushik
, p. 326 - 329 (2012/04/10)
A highly efficient and green protocol for monoacylation of symmetrical diamines and chemoselective acylation of primary amines of unsymmetrical diamines has been developed.
Selective Monoacylation of Symmetrical Diamines via Prior Complexation with Boron
Zhang, Zhongxing,Yin, Zhiwei,Meanwell, Nicholas A.,Kadow, John F.,Wang, Tao
, p. 3399 - 3402 (2007/10/03)
(Equation presented) Pretreatment of a symmetrical primary or secondary diamine with 9-BBN prior to the addition of an acyl chloride significantly suppressed undesired diacylation, and the product of monoacylation predominated. The reactive preference is interpreted as the result of a selective deactivation of one nitrogen atom of the diamine by 9-BBN.
Effective ring-opening reaction of aziridines with trimethylsilyl compounds: A facile access to β-amino acids and 1,2-diamine derivatives
Wu, Jie,Hou, Xue-Long,Dai, Li-Xin
, p. 1344 - 1348 (2007/10/03)
Ring-opening reactions of aziridines with trimethylsilyl compounds triggered by tetrabutylammonium fluoride give the corresponding products regioselectively in excellent yield. It provides a facile and efficient procedure for the ring-opening reactions of
NOVEL, ENANTIOSELECTIVE SYNTHESIS OF VICINAL CYCLOHEXANE-DIAMINES AS KEY-INTERMEDIATES FOR HIGHLY SELECTIVE OPIOID KAPPA AND SIGMA AGONISTS.
Schlichter, Wolfgang H.,Frahm, August W.
, p. 329 - 332 (2007/10/02)
Enantiomers of Cyclohexane-1,2-diamines have been synthesized via two different synthetic approaches by asymmetric catalytic hydrogenation.
