78196-99-3Relevant academic research and scientific papers
Rhodium-Catalyzed Rearrangement of S/Se-Ylides for the Synthesis of Substituted Vinylogous Carbonates
Reddy, Angula Chandra Shekar,Anbarasan, Pazhamalai
supporting information, p. 9965 - 9969 (2019/12/24)
An efficient rhodium-catalyzed unprecedented oxa-[2,3]-sigmatropic rearrangement of sulfur ylide derived from α-thioesters/ketones and diazo carbonyl compounds has been accomplished for the synthesis of various sulfur-tethered vinylogous carbonates in good to excellent yields. Important features of the developed reaction include wide functional group tolerance, excellent chemo- and regioselectivity, and efficient rearrangement involving the carbonyl motif. The present reaction also equally works well with α-selenoesters for the synthesis of seleno-containing vinylogous carbonates.
Visible light mediated reductions of ethers, amines and sulfides
Monos, Timothy M.,Magallanes, Gabriel,Sebren, Leanne J.,Stephenson, Corey R.J.
, p. 240 - 248 (2016/07/21)
Visible light-mediated photoredox catalysis enables the chemoselective reduction of activated carbon–heteroatom bonds as a function of reduction potential. The expansion of the scope of C–X bond reductions towards less activated motifs, such as ethers, amines and sulfides, is important to both organic synthesis and macromolecular degradation method development. In the present report, exploration of photoredox catalysis in alcoholic solvents mediated a decrease in the super-stoichiometric use of iPr2NEt and HCO2H in the reduction of α-keto ethers, amines and sulfides. Additionally, in the absence of fragmentation, [Formula presented] bond formation was afforded, suggesting an intermediate ketyl radicals are present in these transformations.
Rhodium(II) Acetate Catalysed Reactions of 2-Diazo-1,3-indandione and 2-Diazo-1-indanone with Various Substrates
Rosenfeld, M. J.,Shankar, B. K. Ravi,Shechter, H.
, p. 2699 - 2705 (2007/10/02)
Decomposition of 2-diazo-1,3-indandione (3) by rhodium(II) acetate (1) in cyclohexane and in benzene results in overall carbon-hydrogen insertion to give 2-substituted 1,3-indandiones.Anisole, 1, and 3 yield 2-(4-methoxyphenyl)-1,3-indandione (74 percent); benzenes substituted by a single methyl or halogen groups yield the corresponding ortho- and para-substitution products.Spirocyclopropanes are obtained by rhodium(II)-catalyzed additions of 3 to olefins; electron-deficient olefins do not give adducts.Substituted 4H-indenofuran-4-ones and 2,3-disubstituted spiroindene>-1',3'-diones are formed from rhodium(II)-catalyzed reactions of 3 with acetylenes.Reactions of 1 and 3 with cyclohexane, olefins, acetylenes, and arenes involve selective electrophilic carbenic or ylidic processes. 2-Diazo-1-indanone (4) is converted by 1 to 2,2'-bis (48).Thiophenol reacts with 4 and 1 to yield 2-(phenylthio)-1-indanone (49).Cyclopropanations of cyclohexene and styrene by 4 as catalyzed by 1 result in spiroheptane-7,2'-indan>-1-one (50) and 2-phenylspiroinden>-1'(3'H)-one (51), respectively.
Synthesis of 5,6,6a,7,7a,12a-Hexahydro-4H-benzobenzothienoquinolines and of 8-Phenyl-2,3,7,8,9,9a-hexahydro-1H-benzoquinolines
Copp, Frederick C.,Franzmann, Karl W.,Gilmore, Jeremy,Whalley, W. Basil
, p. 909 - 914 (2007/10/02)
Demethylation of 1-(3-benzothienylmethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (1; R=H) gives two diastereoisomeric 1,2-dihydroxy-5,6,6a,7,7a,12a-hexahydro-4H-benzobenzothienoquinolines (4; R=H).Desulphurisation of their N-acetyl-di
A Study of Some Thiophene Analogues of Glycolic Acid
Jeffries, Alfred T.,Moore, Kenneth C.,Ondeyka, Debra M.,Springsteen, Arthur W.,MacDowell, Denis W.H.
, p. 2885 - 2889 (2007/10/02)
Reaction of phenyl(3-thienyl)glycolic acid (1) with AlCl3 in benzene solution leads to the formation of 4H-indenothiophene-4-carboxylic acid (2) whereas analogous reaction of phenyl(2-thienyl)glycolic acid (4) produces no indenothiophene but only a mixture of 5 and 6.In the case of di-(2-thienyl)glycolic acid (14b) and di-(3-thienyl)glycolic acid (16b) analogous results are obtained, with the former leading to the formation of 15 and the latter producing 17.In the case of the (benzothienyl)phenylglycolic analogues of 1 and 4 the acids were unstable to heat so that the esters, ethyl (2-benzothienyl)phenylglycolate (21) and ethyl (3-benzothienyl)phenylglycolate (20), upon treatment with AlCl3 in benzene led to cyclized products only.The former gave 23 which was saponified and decarboxylated to yield 25 and compared with an authentic sample obtained by synthesis.Ester 20 similarly gave 22 which was similarly converted to the known 24.A mechanistic explanation of these findings is proposed.
