Titanium-Catalyzed Hydrohydrazination of Carbodiimides
摘要:
Hydrazinediido complexes of the type [Cp*Ti-(NxylN)(NNR2)(L)] (R = Ph, Me; Ar, fluorene, L = (BuNH2)-Bu-t, Py; 3a-e) have been synthesized and used as catalysts for the hydrohydrazination of a series of carbodiimides, yielding aminoguanidines or fluoreneiminoguanidines. The highest yields were obtained for diarylhydrazines and fluorenone 5 hydrazone at temperatures between 80 and 105 degrees C. Stoichiometric reactions of hydraz inediido complexes with (PrNCNPr)-Pr-i-Pr-i led to an equilibrium with the resulting [2 + 2] cydoadducts 4a-f, which were characterized by H-1, C-13, and N-15 NMR spectroscopy as well as X-ray diffraction. The proposed mechanism, which is closely related to that previously established for the hydrohydrazination of alkynes and allenes, was found to be consistent with the results of a kinetic study. The dynamic structures of aminoguanidines and fluoreneiminoguanidines were characterized by NMR spectroscopy, and the minimum configurations were foud to be stabilized by intramolecular hydrogen bonding.
A palladium-catalyzed C–N bond coupling reaction between arylhydrazines and aryl tosylates for facile synthesis of unsymmetrical N,N-diarylhydrazines has been developed. Employing the catalyst system of Pd(TFA)2 associated with newly developed phosphine ligand L1, the monoarylation of arylhydrazine proceeds smoothly to afford desired products in good-to-excellent yields (up to 95%) with good functional
[EN] PYRAZOLIDINOL COMPOUNDS<br/>[FR] COMPOSES A BASE DE PYRAZOLIDINOLE
申请人:VIRAL AS A
公开号:WO2001000585A1
公开(公告)日:2001-01-04
The invention provides the use of an optionally hydroxy-protected 4-hydroxy or hydroperoxy-3,5-dioxopyrazolidine or an equivalent wherein a pyrazolidine ring attached oxygen is replaced by a sulphur, or a physiologically acceptable salt thereof, for the manufacture of a medicament for use in therapy or prophylaxis. Additionally, the invention provides a method of combatting HIV infection which comprises administering to an HIV-infected patient a T-lymphocyte growth suppressing agent, preferably a pyrazolidinol, in an amount sufficient to suppress T-lymphocyte growth in said patient for a period sufficient to reduce the T-lymphocyte concentration in lymph nodes in said patient by at least 25 % said administration being repeated at intervals of at least 3 months.
Rhodium(<scp>i</scp>)-catalyzed <i>N</i>-arylation of arylazocarboxylates: facile access to unsymmetrical <i>N</i>,<i>N</i>-diarylhydrazides
作者:Xiaofeng Rao、Wei-An Zhang、Ming-Hua Xu
DOI:10.1039/d3nj01022h
日期:——
A simple, efficient, and broad-scope rhodium(I)-catalyzed direct N-arylation of arylazocarboxylates with arylboronic acids has been developed, allowing access to a diverse range of unsymmetrical N,N-diarylhydrazides from readily available starting materials in high yields under extraordinary mild conditions. The reaction features easy operation, ambient temperature and low catalyst loading (as low