10383-90-1Relevant articles and documents
13C NMR study of the carbonylation of benzene with CO in sulfated zirconia
Clingenpeel, T. H.,Wessel, T. E.,Biaglow, A. I.
, p. 5469 - 5470 (1997)
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On the mechanism of addition of lithium pinacolone enolate to benzaldehyde: Polar or electron transfer?
Yamataka, Hiroshi,Sasaki, Daizo,Kuwatani, Yoshiyuki,Mishima, Masaaki,Tsuno, Yuho
, p. 9975 - 9979 (1997)
The carbonyl-carbon kinetic isotope effect (KIE) and the substituent effect were measured for the reaction of lithium pinacolone enolate (CH2=C(OLi)C(CH3)3) with benzaldehyde, and the results were compared with those for other lithium reagents such as MeLi, PhLi, and CH2=CHCH2Li. Ab initio MO calculations (HF/6-31+G*) were carried out to estimate the equilibrium IE on the addition to benzaldehyde. A carbonyl addition reaction, in general, proceeds by way of either a polar direct nucleophilic attack (PL) in a one-step or a two-step process going through a radical ion intermediate (eq 1). The carbonyl-carbon KIE is of primary nature for the PL or the RC rate-determining ET mechanism, while it is considered to be secondary for the ET rate-determining mechanism. The reaction of lithium pinacolone enolate with benzaldehyde gave a small positive KIE (12k/13k = 1.019), which is larger than the theoretical equilibrium IE (12K/13K = 1.006) determined by the MO calculations. Thus, there is a reaction-coordinate contribution to the observed KIE. This is in sharp contrast to the absence of KIE (12k/14k = 1.000) measured previously for the MeLi addition. Dehalogenation and enone-isomerization probe experiments showed no evidence of a single electron transfer to occur during the course of the reaction. The primary carbonyl-carbon KIE together with the substituent effect and chemical probe experiments led to the conclusion that the reaction of lithium pinacolone enolate with benzaldehyde proceeds via the polar mechanism.
BIOSYNTHESIS OF THE BENZOYL MOIETY OF COCAINE FROM CINNAMIC ACID VIA (R)-(+)-3-HYDROXY-3-PHENYLPROPANOIC ACID
Bjorklund, Jeffrey A.,Leete, Edward
, p. 3883 - 3888 (1992)
trans-Cinnamic acid and the N-acetylcysteamine thioester of -trans-cinnamic acid served as precursors of the benzoyl moiety of cocaine when fed to intact Erythroxylum coca plants.The specific incorporation of the thioester in
Rhodium-catalyzed reductive carbonylation of aryl iodides to arylaldehydes with syngas
Chen, Suqing,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong,Yu, Dongkun,Zhao, Xinhui
, p. 645 - 656 (2020/05/14)
The reductive carbonylation of aryl iodides to aryl aldehydes possesses broad application prospects. We present an efficient and facile Rh-based catalytic system composed of the commercially available Rh salt RhCl3·3H2O, PPh3 as phosphine ligand, and Et3N as the base, for the synthesis of arylaldehydes via the reductive carbonylation of aryl iodides with CO and H2 under relatively mild conditions with a broad substrate range affording the products in good to excellent yields. Systematic investigations were carried out to study the experimental parameters. We explored the optimal ratio of Rh salt and PPh3 ligand, substrate scope, carbonyl source and hydrogen source, and the reaction mechanism. Particularly, a scaled-up experiment indicated that the catalytic method could find valuable applications in industrial productions. The low gas pressure, cheap ligand and low metal dosage could significantly improve the practicability in both chemical researches and industrial applications.
Metathesis Reaction of Diazo Compounds and para-Quinone Methides for C-C Double Bond Formation: Synthesis of Tetrasubstituted Alkenes and Quinolinones
Huang, Bo,Shen, Yangyong,Mao, Zhenjun,Liu, Yu,Cui, Sunliang
, p. 4888 - 4891 (2016/10/18)
The para-quinone methides (p-QMs) are activated by Lewis acid and then attacked by diazo compounds. The following rearrangement leads to nitrogen gas extrusion and C-C double bond formation to constitute a metathesis reaction process. Therefore, the diazo
Gold-catalyzed 1,3-transposition of ynones
Kazem Shiroodi, Roohollah,Soltani, Mohammad,Gevorgyan, Vladimir
, p. 9882 - 9885 (2014/08/05)
An efficient, regioselective gold-catalyzed 1,3-transposition reaction of ynones and diynones has been developed. It was found that stereoelectronic (interrupted conjugation) and electronic (extended conjugation) factors could efficiently govern the regio