290333-90-3Relevant academic research and scientific papers
The AZARYPHOS family of ligands for ambifunctional catalysis: Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes
Hintermann, Lukas,Dang, Tuan Thanh,Labonne, Aurelie.,Kribber, Thomas,Xiao, Li,Naumov, Pance
supporting information; experimental part, p. 7167 - 7179 (2010/02/28)
The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPY-PHOS), 4,6-disubsituted l,3-diazin-2ylphosphanes or l,3,5-triazin-2- ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)2(MeCN)][PF6] (Cp = cyclopentadieny1)gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.
A general and selective copper-catalyzed cross-coupling of tertiary grignard reagents with azacyclic electrophiles
Hintermann, Lukas,Xiao, Li,Labonne, Aurelie
supporting information; experimental part, p. 8246 - 8250 (2009/04/13)
(Chemical Equation Presented) Bulky heterocycles: A highly selective catalytic cross-coupling reaction of tertiary Grignard reagents with chloroazacycles provides a shortcut to heterocyclic building blocks for applications in pharmaceutical chemistry and supramolecular chemistry, or as ligand precursors in transition-metal catalysis (see scheme).
A general bifunctional catalyst for the anti-Markovnikov hydration of terminal alkynes to aldehydes gives enzyme-like rate and selectivity enhancements
Grotjahn, Douglas B.,Lev, Daniel A.
, p. 12232 - 12233 (2007/10/03)
A new, bifunctional catalyst for anti-Markovnikov hydration of terminal alkynes to aldehydes (6) allows practical room-temperature hydration of alkyl-substituted alkynes. Other outstanding features include near-quantitative aldehyde yields from both alkyl- and aryl-substituted alkynes and wide functional group tolerance. The uncatalyzed rate of alkyne hydration is measured for the first time, showing the enzyme-like rate and selectivity enhancements of aldehyde formation by 6. For aldehyde formation, an uncatalyzed rate -10 mol h-1 means a half-life >600 000, years. The catalyzed rate is up to 23.8 mol (mol 6)-1 h-1 and 10 000:1 ratio in favor of aldehyde. Changes in rate and selectivity induced by 6 are thus >2.4 × 1011 and 300 000, respectively. Copyright
The chemistry of new nitrosyltungsten complexes with pyridyl- functionalized phosphane ligands
Baur, Juergen,Jacobsen, Heiko,Burger, Peter,Artus, Georg,Berke, Heinz,Dahlenburg, Lutz
, p. 1411 - 1422 (2007/10/03)
The coordination chemistry of pyridylphosphanes, such as 2(6-tert- butylpyridyl)diphenylphosphane (Ph2P-tert-Bupy) (6) and 2-(6-tert- butylpyridyl)dimethylphosphane (Me2P-tert-Bupy) (7) towards a number of nitrosyltungsten complexes is reported. Displacement of the loosely coordinated MeCN from [W(CH3CN)3(CO)2(NO)][BF4] led to the following cationic compounds incorporating mono- and bidentate coordinated phosphane ligands: cis,cis-[W(CO)2(NO)(Ph2PR)(η2-Ph2PR)][BF4], [R = 2-pyridyl (9a), 2-picolyl (11)], cis,cis-[W(CO)(NO)(η2-Ph2Ppy)2][BF4] (20), trans,trans-[W(CO)(NO)(η2-Ph2Ppy)2][BPh4] (21), fac-[W(CO)2(NO) (Me2P- py)3][BF4] (16), fac-[W(CO)2(NO)(Me2P-tert-Bupy)3][BF4] (18), cis,cis- [W(CO)2(NO)(Me2Ppy)(η2-Me2Ppy)][BF4] (22), and cis,cis- [W(CO)2(CH3CN)(NO)(Me2P-tert-Bupy)2][BF4] (23a). The cationic complex cis,mer-[W(CO)3(NO)(Ph2P-tert-Bupy)2][PF6] (14) has been prepared by nitrosylation of cis/trans-W(CO)4(Ph2P-tert-Bupy)2 (13). Reactions of 9a, 11, 14, 16, and 18 with hydride transfer reagents afforded trans,- trans- HW(CO)2(NO)(Ph2Ppy)2 (10), trans, trans-HW(CO)2(NO)(Ph2Ppic)2 (12), trans, trans-HW(CO)2(NO)(Ph2-tBupy)2 (15), cis/trans- HW(CO)2(NO)(Me2Ppy)2 (17), and cis/trans-HW(CO)2(NO)(Me2P-tert-Bupy)2 (19), respectively. Reactivity experiments with acetic acid, hydroiodic acid, carbon dioxide, and acetylenedicarboxylic acid were performed, and were found to afford trans-W(CO)(NO)(Ph2Ppy)2(η2-CH3CO2) (24), trans, trans- IW(CO)2(NO)(Ph2Ppy)2 (25), trans-W(HCO2)(CO)2(NO)(Ph2Ppy)2 (26), and trans-W{η2-(Z)C(CO2Me)=CH[C(O)OMe]}(CO)(NO)(Ph2Ppic)2 (27), respectively. The influence of the pyridyl substituent in 10 was probed by a comparative H/D exchange experiment in which 10 and the analogous complex HW(CO)2(NO)(PPh3)2 were treated with MeOD. The deuterated complex trans,trans-WD(CO)2(NO)(Ph2Ppy)2 (28) could be isolated. The structures of 9a, 11, 14, and 20 have been determined by single-crystal X-ray diffraction analysis.
