5667-03-8Relevant articles and documents
Rh-Catalyzed Asymmetric Hydrogenation of Unsaturated Medium-Ring NH Lactams: Highly Enantioselective Synthesis of N-Unprotected 2,3-Dihydro-1,5-benzothiazepinones
Yin, Congcong,Yang, Tao,Pan, Yingmin,Wen, Jialin,Zhang, Xumu
, p. 920 - 923 (2020/02/04)
A straightforward method to prepare 1,5-benzothiazepines was reported. Catalyzed by a Rh/Zhaophos complex, unsaturated cyclic NH lactams with a medium-size ring were hydrogenated smoothly, giving remarkably high enantioselectivities. The sulfur atom in the substrates did not bring an inhibition which was observed with commercially available bisphosphine ligands. This method was successfully applied in the scale-up synthesis of (R)-(-)-thiazesim.
Unexpected Reaction Pathways in the Reaction of Alkoxyalkynyl-chromium(0) Carbenes with Aromatic Dinucleophiles
Sierra, Miguel A.,Mancheno, Maria J.,Del Amo, Juan C.,Fernandez, Israel,Gomez-Gallego, Mar
, p. 4943 - 4953 (2007/10/03)
Thermal- or SiO2-induced reactions of the Michael adducts of 1,2-aromatic dinucleophiles and alkynyl-chromium(0) carbene complexes, compounds 7-10, form different products in good yields depending on the nature of the aromatic dinucleophile used. Thus, 1,2-diaminobenzene derivatives 7 and 8 rearrange to pentacarbonylchromium(0) isocyanide complexes 11, 12, 14, and 15 in a process that occurs through bicyclic intermediates 24. Adducts 9 derived from o-aminophenol give 2,3-dihydro-1,5-benzoxazepine derivatives 17 by intramolecular 1,2-addition, followed by protonation at the chromium center and reductive elimination. In contrast, base-promoted addition of the phenolic hydroxy group in compound 9a affords 3-ethoxy-5-phenyl-5,6-dihydro-2H-1,6-benzoxazocin-2-one (18), together with the expected adduct 17a. Compound 18 is formed by a nucleophilic addition to a CO ligand in a preformed carbene complex. This is a new example of the rare attack of a nucleophile on a CO ligand in a Fischer carbene complex. Adducts 10 form seven-membered-ring carbene complexes 19 and 20 by intramolecular aminolysis. In contrast, reaction of alkynyl carbene complexes with 1,8-diaminonaphthalene under very mild conditions leads to 2-substituted perimidines 33 together with the corresponding ethoxymethylmetal carbene complex 32 through an unprecedented fragmentation process in a formal retro-Aumann reaction.
Note on the Synthesis, Properties, and Reactions of 4-Methoxy-2-phenyl-1,5-benzothiazepine
Hofmann, Hans,Fischer, Herbert,Bremer, Matthias
, p. 2087 - 2089 (2007/10/02)
The title compound 3 is synthesized by O-alkylation of the corresponding lactam 1.The behaviour of 3 is different from a compound with the same formula which has been published recently in this journal; the structure of 3 therefore was confirmed by X-ray