The asymmetric hydrogenation (AH) of cyclic -alkyl imines offers an elegant and efficient method to afford chiral amines, especially for -nicotine and its derivatives. However, this approach remains an ongoing challenge due to undesirable coordination of pyridyl-containing substrates to the active metal catalyst. Herein, we disclose a manganese-catalyzed AH that allows access to -nicotine and other chiral α-(hetero)aryl pyrrolidines and provides an example of a base-metal catalyst that displays superior performance to its noble metal counterparts.
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http://dx.doi.org/10.1021/acs.orglett.5c00044 | DOI Listing |
Acta Crystallogr E Crystallogr Commun
March 2025
Department of Chemistry, Bahir Dar University, PO Box 79, Bahir Dar, Ethiopia.
The asymmetric unit of the title salt, CHFNSe·Cl, contains one planar 4-fluoro-benzo[][1,2,5]selena-diazol-1-ium mol-ecular cation and a chloride anion. In the crystal, inter-molecular N-H⋯Cl hydrogen bonds link the 4-fluoro-benzo[][1,2,5]selena-diazol-1-ium mol-ecules, which are arranged in parallel layers along (104), to the chloride anions. The cationic layers, in turn, are stacked along [001].
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
March 2025
Toyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan.
The asymmetric unit of the title compound, {[Co(CHO)(HO)]·2CHNO} or {[Co(Hdondc)(HO)]·2DMF} , comprises half of a Co ion, half of a 1,5-di-hydroxy-naphthalene-2,6-di-carboxyl-ate dianion (Hdondc), two water mol-ecules and a di-methyl-formamide (DMF) mol-ecule. The Co ion, which is located on a crystallographic inversion center, exhibits a distorted six-coord-inated octa-hedral geometry with two oxygen atoms of the Hdondc ligand and four oxygen atoms of the water mol-ecules. The carboxyl-ate group is almost coplanar with the naphthalene moiety and shows monodentate coordination to the Co ion.
View Article and Find Full Text PDFActa Crystallogr E Crystallogr Commun
March 2025
A new cobalt complex, bis-[tris-(amino-thio-urea)cobalt(III)] bis-[2-(carb-oxy-methyl)-2-hy-droxy-butane-dioato]cobalt(II) tetra-nitrate tetra-hydrate, [Co(CHNS)][Co(CHO)](NO)·2HO, designated as [Co(tsc)][Co(cit)](NO)·4HO, was synthesized. Two crystallographically independent cobalt centers are present. In the first, the central metal atom is chelated by three thio-semicarbazide ligands in a bidentate fashion whereas the second, positioned on a crystallographic inversion center, is hexa-coordinated by two citrate anions in a distorted octa-hedral geometry.
View Article and Find Full Text PDFOrg Lett
March 2025
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
The asymmetric hydrogenation (AH) of cyclic -alkyl imines offers an elegant and efficient method to afford chiral amines, especially for -nicotine and its derivatives. However, this approach remains an ongoing challenge due to undesirable coordination of pyridyl-containing substrates to the active metal catalyst. Herein, we disclose a manganese-catalyzed AH that allows access to -nicotine and other chiral α-(hetero)aryl pyrrolidines and provides an example of a base-metal catalyst that displays superior performance to its noble metal counterparts.
View Article and Find Full Text PDFOrg Lett
March 2025
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
The asymmetric -selective hydrogenation of arenes has long been a significant challenge. In this work, we were able to control the / selectivity in ruthenium-catalyzed asymmetric hydrogenation of 2,3-disubstituted quinoxalines by varying the catalyst counteranion. Using density functional theory calculations, we investigated the weak interactions─such as CH/π and hydrogen bonding─among the counteranion, the catalyst framework, and the substrate, elucidating the fundamental influence of counteranions on / selectivity in the asymmetric hydrogenation of quinoxalines.
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