71172-42-4Relevant articles and documents
A N-Phosphinoamidinato NHC-Diborene Catalyst for Hydroboration
Fan, Jun,Mah, Jian-Qiang,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
, p. 4993 - 5002 (2021/02/01)
The use of the N-phosphinoamidinato NHC-diborene catalyst 2 for hydroboration is described. The N-phosphinoamidine tBu2PN(H)C(Ph)= N(2,6-iPr2C6H3) was reacted with nBuLi in Et2O to afford the lithium derivative, which was then treated with B2Br4(SMe2)2 in toluene to form the N-phosphinoamidinate-bridged diborane 1. It was reacted with the N-heterocyclic carbene IMe (:C{N(CH3)C(CH3)}2) and excess potassium graphite at room temperature in toluene to give the N-phosphinoamidinato NHC-diborene compound 2. It can stoichiometrically activate ammonia-borane and carbon dioxide. It also showed catalytic capability. A 2 mol % portion of 2 catalyzed the hydroboration of carbon dioxide (CO2) with pinacolborane (HBpin) in deuterated benzene (C6D6) at 110 °C (conversion >99%), which afforded the methoxyborane [pinBOMe] (yield 97.8%, TOF 33.3 h-1) and the bis(boryl) oxide [(pinB)2O]. In addition, 5 mol % of 2 catalyzed the N-formylation of secondary and primary amines by carbon dioxide and pinacolborane to yield the N-formamides (average yield 91.6%, TOF 25.9 h-1). Moreover, 2 showed chemoselectivity toward catalytic hydroboration of carbonyl compounds. In mechanistic studies, the B= B double bond in compound 2 activated the substrates, the intermediates of which then underwent hydroboration with pinacolborane to yield the products and regenerate catalyst 2.
Formylation with supercritical carbon dioxide over Ru/Al2O 3 modified by phosphines: Heterogeneous or homogeneous catalysis?
Rohr, Markus,Grunwaldt, Jan-Dierk,Baiker, Alfons
, p. 144 - 153 (2007/10/03)
The formylation of 3-methoxypropylamine with hydrogen and supercritical carbon dioxide over Ru-based catalysts was studied. In this solventless process, carbon dioxide acts as both reactant and solvent. Interestingly, Ru/Al2O3 modified by the phosphine 1,2-bis(diphenylphosphino)ethane (dppe) showed a high formylation activity at 100% selectivity, comparable to those of the homogeneous catalysts RuCl 2(dppe)2 and RuCl2(PPh3) 3. Analysis of the reaction mixture by ICP-OES and structural studies by in situ X-ray absorption spectroscopy discovered that the presence of the phosphine modifier led to the formation of a homogeneous ruthenium catalyst.
Long-range anisotropic effects of long chain amides
Budzikiewicz, Herbert,Vieth, Peter-Eric,Krueger, Uwe
, p. 825 - 840 (2007/10/02)
In 1H-NMR spectra of amids with long-chain aliphatic N-substituents one observes - despite of the free mobility of the aliphatic chain - splitting of the signals of the terminal methyl groups which is caused by the hindered rotation of the amide bond. - Keywords: Amides; Hindered rotation; 1H-NMR