98195-34-7Relevant academic research and scientific papers
Formate as a CO surrogate for cascade processes: Rh-catalyzed cooperative decarbonylation and asymmetric Pauson-Khand-type cyclization reactions
Lee, Hang Wai,Chan, Albert S. C.,Kwong, Fuk Yee
, p. 2633 - 2635 (2008/02/08)
A rhodium-(S)-xyl-BINAP complex-catalyzed tandem formate decarbonylation and [2 + 2 + 1] carbonylative cyclization is described; this cooperative process utilizes formate as a condensed CO source, and the newly developed cascade protocol can be extended t
N-dealkylation of an N-cyclopropylamine by horseradish peroxidase. Fate of the cyclopropyl group
Shaffer,Morton,Hanzlik
, p. 8502 - 8508 (2007/10/03)
Cyclopropylamines inactivate cytochrome P450 enzymes which catalyze their oxidative N-dealkylation. A key intermediate in both processes is postulated to be a highly reactive aminium cation radical formed by single electron transfer (SET) oxidation of the nitrogen center, but direct evidence for this has remained elusive. To address this deficiency and identify the fate of the cyclopropyl group lost upon N-dealkylation, we have investigated the oxidation of N-cyclopropyl-N-methylaniline (3) by horseradish peroxidase, a well-known SET enzyme. For comparison, similar studies were carried out in parallel with N-isopropyl-N-methylaniline (9) and N,N-dimethylaniline (8). Under standard peroxidatic conditions (HRP, H2O2, air), HRP oxidizes 8 completely to N-methylaniline (4) plus formaldehyde within 15-30 min, whereas 9 is oxidized more slowly (14C]-3, [1′-13C]-3, and [2′,3′-13C]-3 as substrates, radiochemical and NMR analyses of incubation mixtures revealed that the complete oxidation of 3 by HRP yields 4 (0.2 mol), β-hydroxypropionic acid (17, 0.2 mol), and N-methylquinolinium (16, 0.8 mol). In buffer purged with pure O2, the complete oxidation of 3 yields 4 (0.7 mol), 17 (0.7 mol), and 16 (0.3 mol), while under anaerobic conditions, 16 is formed quantitatively from 3. These results indicate that the aminium ion formed by SET oxidation of 3 undergoes cyclopropyl ring fragmentation exclusively to generate a distonic cation radical (14+?) which then partitions between unimolecular cyclization (leading, after further oxidation, to 16) and bimolecular reaction with dissolved oxygen (leading to 4 and 17 in a 1:1 ratio). Neither β-hydroxypropionaldehyde, acrolein, nor cyclopropanone hydrate are formed as SET metabolites of 3. The synthetic and analytical methods developed in the course of these studies should facilitate the application of cyclopropylamine-containing probes to reactions catalyzed by cytochrome P450 enzymes.
Reactions of ruthenium carbenes of the type (PPh3)2(X)2Ru=CH - CH=CPh2 (X = Cl and CF3COO) with strained acyclic olefins and functionalized olefins
Wu, Zhe,Nguyen, Sonbinh T.,Grubbs, Robert H.,Ziller, Joseph W.
, p. 5503 - 5511 (2007/10/02)
Ruthenium carbene complexes of the type (PPh3)2(X)2Ru=CH - CH=CPh2 (1, X = Cl; 2, X = CF3COO) can react with strained acyclic olefins and functionalized olefins. Complex 1 reacts with methylenecyclopr
Synthesis and Characterization of Diethynylmethanobuckminsterfullerene, a Building Block for Macrocyclic and Polymeric Carbon Allotropes
An, Yi-Zhong,Rubin, Yves,Schaller, Christophe,McElvany, Stephen W.
, p. 2927 - 2929 (2007/10/02)
Diethynylmethanobuckminsterfullerene (1a and 13C-labeled 1b) has been prepared by reaction of the lithium salt of 1,5-bis(trimethylsilyl)-1,4-pentadiyn-3-one (p-toluenesulfonyl)hydrazone (5a/b) with C60 followed by desilylation and characterized by NMR, IR, UV-vis, and CI-TQMS spectroscopies.
Rotational Dynamics of Flexible Alkanes. An NMR Coupled Relaxation and a Brownian Dynamics Study
Brown, Mark S.,Grant, David M.,Horton, W. J.,Mayne, Charles L.,Evans, Glenn T.
, p. 6698 - 6707 (2007/10/02)
The selectively labeled nonanes C4D9(13)CH2C4D9 and C7D15(13)CH2CD3 and the heneicosane C10D21(13)CH2C10D21 have been synthesized and the spin-lattice relaxations of the isolated 13CH2 groups studied by carbon-13 NMR coupled relaxation methods.Selective a
