593-60-2Relevant academic research and scientific papers
Radical Carbonyl Propargylation by Dual Catalysis
Huang, Huan-Ming,Bellotti, Peter,Daniliuc, Constantin G.,Glorius, Frank
supporting information, p. 2464 - 2471 (2020/12/07)
Carbonyl propargylation has been established as a valuable tool in the realm of carbon–carbon bond forming reactions. The 1,3-enyne moiety has been recognized as an alternative pronucleophile in the above transformation through an ionic mechanism. Herein, we report for the first time, the radical carbonyl propargylation through dual chromium/photoredox catalysis. A library of valuable homopropargylic alcohols bearing all-carbon quaternary centers could be obtained by a catalytic radical three-component coupling of 1,3-enynes, aldehydes and suitable radical precursors (41 examples). This redox-neutral multi-component reaction occurs under very mild conditions and shows high functional group tolerance. Remarkably, bench-stable, non-toxic, and inexpensive CrCl3 could be employed as a chromium source. Preliminary mechanistic investigations suggest a radical-polar crossover mechanism, which offers a complementary and novel approach towards the preparation of valuable synthetic architectures from simple chemicals.
PROCESS FOR THE PRODUCTION OF FERROPORTIN INHIBITORS
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Page/Page column 33-34; 43-46, (2021/10/02)
The invention relates to a new process for preparing compounds of the formula (I) and pharmaceutically acceptable salts thereof, which act as ferroportin inhibitors being suitable for the use as medicaments in the prophylaxis and/or treatment of diseases caused by a lack of hepcidin or of iron metabolism disorders leading to increased iron levels or increased iron absorption, including iron overload, thalassemia, sickle cell disease and hemochromatosis.
Compounds and methods for the reduction of halogenated hydrocarbons
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Page/Page column 19, (2017/12/27)
The present application relates to methods for the reduction of halogenated hydrocarbons using compounds of Formula (I): wherein the reduction of the halogenated compounds is carried out, for example, under ambient conditions without the need for a transition metal containing co-factor. The present application also relates to methods of recovering precious metals using compounds of Formula (I) that are absorbed onto a support material.
Ultrasonically Assisted Decarboxylative Bromination of α,β-Unsaturated Carboxylic Acids under Vilsmeier-Haack Conditions
Kumar, M. Satish,Rajanna,Venkanna,Venkateswarlu,Sudhakar Chary
, p. 642 - 646 (2015/12/26)
An efficient method for decarboxylative bromination of cinnamic acids (α,β-unsaturated carboxylic acids or 3-arylpropenoic acids) was achieved under relatively mild conditions using Vilsmeier-Haack reagent and KBr in acetonitrile media. Vilsmeier-Haack reagent is prepared by using 1:1 ratio of oxychloride (SOCl2 or POCl3) and DMF under chilled condition. Ultrasonically assisted reactions underwent smoothly with highly significant rate enhancements and afforded bromostyrenes as products in very good yields even though the reactions were too sluggish.
Synthetic methods and intermediates for the preparation of xenicanes
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Page/Page column, (2014/09/03)
The invention provides novel synthetic intermediates and synthetic methods that are useful for preparing compounds of the xenicane family. Certain compounds of the invention may also possess anti-cancer properties.
Total synthesis and biological evaluation of (-)-9-deoxy-englerin a
Ushakov, Dmitry B.,Navickas, Vaidotas,Strobele, Markus,Maichle-Moessmer, Caecilia,Sasse, Florenz,Maier, Martin E.
supporting information; experimental part, p. 2090 - 2093 (2011/06/22)
An effective total synthesis of (-)-9-deoxy-englerin (4), an analogue of the natural guaiane sesquiterpene englerin A (1), has been achieved. The synthesis features a transannular epoxide opening to construct the 5,7-fused ring system followed by transannular ether formation with mercury(II) trifluoroacetate.
Unimolecular reactions of CH2BrCH2Br, CH 2BrCH2Cl, and CH2BrCD2Cl: Identification of the Cl-Br interchange reaction
Friederich, Laura,Duncan, Juliana R.,Heard, George L.,Setser,Holmes, Bert E.
experimental part, p. 4138 - 4147 (2010/09/04)
The recombination reactions of CH2Br and CH2Cl radicals have been used to generate vibrationally excited CH 2BrCH2Br and CH2BrCH2Cl molecules with 91 kcal mol-1 of energy in a room-temperature bath gas. The experimental unimolecular rate constants for elimination of HBr and HCl were compared to calculated statistical rate constants to assign threshold energies of 58 kcal mol-1 for HBr elimination from C2H 4Br2 and 58 and 60 kcal mol-1, respectively, for HBr and HCl elimination from C2H4BrCl. The Br-Cl interchange reaction was demonstrated and characterized by studying the CH 2BrCD2Cl system generated by the recombination of CH 2Br and CD2Cl radicals. The interchange reaction was identified from the elimination of HBr and DCl from CH2ClCD 2Br. The interchange reaction rate is much faster than the rates of either DBr or HCl elimination from CH2BrCD2Cl, and a threshold energy of ?43 kcal mol-1 was assigned to the interchange reaction. The statistical rate constants were calculated from models of the transition states that were obtained from density functional theory using the B3PW91 method with the 6-31G(d′,p′) basis set. The model for HBr elimination was tested versus published thermal and chemical activation data for C2H5Br. A comparison of Br-Cl interchange with the Cl-F and Br-F interchange reactions in 1,2-haloalkanes is presented.
Pyrolysis of α- and β-heteroatoms substituted ethyl phenyl sulfoxides
Yoshimura, Toshiaki,Sakae, Hironori,Yoshizawa, Masaki,Hasegawa, Kiyoshi,Tsukurimichi, Eiichi
experimental part, p. 1162 - 1173 (2010/08/06)
A study on the mechanism of the thermal decomposition of α- and β-heteroatoms substituted ethyl phenyl sulfoxides was carried out using 1-chloroethyl phenyl sulfoxide (1); two diastereomeric 1-acetoxyethyl (substituted phenyl) sulfoxides (2a) and (2b); and 2-chloroethyl phenyl, 2-bromoethyl phenyl, and 2-methoxyethyl phenyl sulfoxides (3, 4, 5). The rate of pyrolysis of 1 was 4.8 times faster at 160°C than that of ethyl phenyl sulfoxide used as a reference, while those of 2a and 2b were 107 and 155 times faster, respectively. The results indicate that the lone pair of electrons on the α-heteroatoms has a larger rate acceleration effect than the electronegativity of them. The substituent effects of the phenyl group of 2a and 2b gave positive Hammett ρ-values (ρa= 0.76 and ρb= 0.80 vs. σ). Activation parameters for 2a and 2b are as follows: 2a, ΔH?= 112 kJmol-1, ΔS?= -20 JK-1mol-1; 2b, ΔH?= 107 kJmol-1, ΔS?= -29 JK-1mol-1. Large deuterium kinetic isotope effects for 1-acetoxyethyl-2,2,2-d3 phenyl sulfoxides (2ad and 2bd) were observed (kH/kD= 3.5 ～ 4.1). These results suggest that the pyrolysis of -heteroatom substituted ethyl phenyl sulfoxides proceeds via a five-membered transition state deviated to E1-like in character. On the other hand, from the results of kinetics for the pyrolysis of 3, 4, and 5, no effect by the β-halogen atoms or some deceleration effect by the β-methoxy group was observed. Thus the reaction seems to proceed via an E1-like mechanism. Copyright Taylor & Francis Group.
Synthesis of sulfur-containing aryl and heteroaryl vinyls via Suzuki-Miyaura cross-coupling for the preparation of SERS-active polymers
Perez-Pineiro, Rolando,Dai, Sheng,Alvarez-Puebla, Ramon,Wigginton, James,Al-Hourani, Baker Jawabrah,Fenniri, Hicham
supporting information; experimental part, p. 5467 - 5469 (2010/01/11)
The preparation of sulfur-containing aryl and heteroaryl vinyl co-monomers via Suzuki-Miyaura cross-coupling between the corresponding mercaptomethyl arylboronates and in situ-generated vinyl bromides is described. Surface-enhanced Raman scattering (SERS) studies of the target compounds on gold nanoparticles confirmed their potential as spectroscopic tags in the fabrication of SERS-encoded polymers for combinatorial screening and biomedical diagnostics.
Synthesis of hydroxylated hydrocarbons
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Page/Page column 5, (2008/06/13)
Ethylene glycol, other diols, triols, and polyols are made in an efficient manner by reacting dibromides with water in the presence of a metal oxide. An integrated process of dibromide formation, alcohol synthesis, metal oxide regeneration, and bromine recycling is also provided.
