16343-36-5Relevant academic research and scientific papers
Lewis Acid Assisted Electrophilic Fluorine-Catalyzed Pinacol Rearrangement of Hydrobenzoin Substrates: One-Pot Synthesis of (±)-Latifine and (±)-Cherylline
Shi, Hui,Du, Chuan,Zhang, Xinhang,Xie, Fukai,Wang, Xiaoyu,Cui, Shanshan,Peng, Xiaoshi,Cheng, Maosheng,Lin, Bin,Liu, Yongxiang
, p. 1312 - 1319 (2018/02/09)
A microwave-irradiated solvent-free pinacol rearrangement of hydrobenzoin substrates catalyzed by a combination of N-fluorobenzenesulfonimide and FeCl3·6H2O was developed. Its selectivity was first investigated by density functional theory (DFT) calculations. Then the functional group tolerance was examined by synthesizing a series of substrates designed based on the insight provided by the DFT calculations. The application of the methodology was demonstrated by the efficient one-pot synthesis of (±)-latifine and (±)-cherylline, both are 4-aryltetrahydroisoquinoline alkaloids isolated from Amaryllidacecae plants.
α,α-Diarylethylene Glycols as Valuable Precursor for Synthesis of 1,1-Diarylethenes and α,α-Diaryl Acetaldehydes
Tiwari, Praveen Kumar,Sivaraman, Balasubramaniam,Aidhen, Indrapal Singh
supporting information, p. 3594 - 3605 (2017/07/22)
Towards assembling of diarylmethine unit present in biologically important molecules, we have developed a new Weinreb Amide (WA) based building block derived from glycolic acid. The WA functionality present in this building block permits the sequential addition of various arylmagnesium bromide reagents in a controlled manner that enables assembly of a diarylmethine unit. The developed synthetic route provides easy access to important diarylethenes and α,α-diarylethylene glycols. The synthesized α,α-diarylethylene glycols provide access to synthetically important symmetrical and unsymmetrical α,α-diaryl acetaldehydes as valuable intermediates.
Catalytic, regioselective, and green methods for rearrangement of 1,2-diaryl epoxides to carbonyl compounds employing metallic triflates, Br?nsted-acidic ionic liquids (ILs), and IL/microwave; experimental and computational substituent effect study on aryl versus hydrogen migration
Jamalian, Arezu,Rathman, Benjamin,Borosky, Gabriela L.,Laali, Kenneth K.
, p. 1 - 11 (2015/09/28)
The Lewis-acid catalyzed rearrangement of parent trans-stilbene oxide 1 was studied with M(OTf)3/DCM and M(OTf)3/[BMIM][BF4] (M = Bi, Al, Ga, Sc, and Yb; [BMIM] = butylmethylimidazolium) and Zn(NTf2)2, and with Bi(OTf)3/[BMIM][X] (X = NTf2, OTf, PF6, and BF4), employing 5 mol% of catalyst. Selective formation of 2,2-dipheylacetaldehyde 2 (phenyl migration product) was observed in all cases, with Bi(OTf)3 proving most efficient. The rearrangement of 1 was also effected in [BMIM][X] (X = NTf2, OTf, PF6, and BF4) without an added catalyst under microwave MW irradiation, and X = PF6 gave the highest yield and selectivity. Efficient and selective rearrangement of 1-2 was also observed with 0.1-0.3equiv. of [BMIM(SO3H)][OTf] in DCM and in [BMIM][X]. A substituent effect study was performed with a series of singly substituted 1,2-diphenyl oxiranes (with X = OMe, Me, F, CN, and NO2) with 5mol% Bi(OTf)3 in DCM and in [BMIM][NTf2]. Notable formation of ketones was observed with the NO2 and CN derivatives. Competing formation of ketones was also observed in [BMIM][PF6] under MW and under Br?nsted acid catalysis with [BMIM(SO3H)][OTf] in DCM and in [BMIM][NTf2]. The aryl versus H migration was studied computationally by DFT and MP2 methods and by including solvation effects (IEFPCM).
Catalytic, regioselective, and green methods for rearrangement of 1,2-diaryl epoxides to carbonyl compounds employing metallic triflates, Br?nsted-acidic ionic liquids (ILs), and IL/microwave; Experimental and computational substituent effect study on aryl versus hydrogen migration
Jamalian, Arezu,Rathman, Benjamin,Borosky, Gabriela L.,Laali, Kenneth K.
, p. 1 - 11 (2014/11/08)
The Lewis-acid catalyzed rearrangement of parent trans-stilbene oxide 1 was studied with M(OTf)3/DCM and M(OTf)3/[BMIM][BF 4] (M = Bi, Al, Ga, Sc, and Yb; [BMIM] = butylmethylimidazolium) and Zn(NTf2)2, and with Bi(OTf)3/[BMIM][X] (X = NTf2, OTf, PF6, and BF4), employing 5 mol% of catalyst. Selective formation of 2,2-dipheylacetaldehyde 2 (phenyl migration product) was observed in all cases, with Bi(OTf)3 proving most efficient. The rearrangement of 1 was also effected in [BMIM][X] (X = NTf 2, OTf, PF6, and BF4) without an added catalyst under microwave MW irradiation, and X = PF6 gave the highest yield and selectivity. Efficient and selective rearrangement of 1-2 was also observed with 0.1-0.3 equiv. of [BMIM(SO3H)][OTf] in DCM and in [BMIM][X]. A substituent effect study was performed with a series of singly substituted 1,2-diphenyl oxiranes (with X = OMe, Me, F, CN, and NO2) with 5 mol% Bi(OTf)3 in DCM and in [BMIM][NTf2]. Notable formation of ketones was observed with the NO2 and CN derivatives. Competing formation of ketones was also observed in [BMIM][PF6] under MW and under Br?nsted acid catalysis with [BMIM(SO3H)][OTf] in DCM and in [BMIM][NTf2]. The aryl versus H migration was studied computationally by DFT and MP2 methods and by including solvation effects (IEFPCM).
Weinreb amide based building blocks for convenient access to 1,1-diarylethenes and isocombretastatin analogues
Balasubramaniam, Sivaraman,Kommidi, Harikrishna,Aidhen, Indrapal Singh
, p. 2683 - 2686 (2011/06/19)
A successful strategy based on the synthetic equivalent containing Weinreb amide functionality for the convenient access to 1,1-diarylethenes in general and for the isocombretastatin analogues in particular has been developed from the commercially available glyoxalic acid. The convenience with which the structural variations can be made in assembling the aryl residues shows generality associated with the developed strategy. The intermediates also provide access to 1,2,2-triarylethanones, represented by the synthesis of advanced intermediate of tamoxifen.
Aryl(chloro)methyl 4-tolyl sulfoxides: Synthesis and application to the synthesis of α-aryl ketones
Fukuda, Shigehiko,Tsuji, Kazuhito,Musashi, Jun,Nonaka, Ryo,Kimura, Tsutomu,Satoh, Tsuyoshi
, p. 3615 - 3626 (2011/12/16)
Aryl(chloro)methyl 4-tolyl sulfoxides were synthesized from arylmethyl 4-tolyl sulfoxides in moderate-to-good yields by sequential treatment with lithium diisopropylamide and tosyl chloride at low temperatures. Treatment of the lithium α-sulfinyl carbanion of the aryl(chloro)methyl 4-tolyl sulfoxides with aldehydes or ketones resulted in the formation of adducts in good-to-high yields. Treatment of these adducts with tert-butylmagnesium chloride gave the corresponding magnesium alkoxides. On treatment with isopropylmagnesium chloride, the alkoxides gave the corresponding magnesium β-oxido carbenoids, which rearranged to give α-aryl ketones in good-to-high yields. The magnesium enolate intermediates generated by rearrangement of the -oxido carbenoids could also be trapped with electrophiles to give α-aryl α-substituted ketones. These procedures offer a good method for the synthesis of a variety of α-aryl ketones from aldehydes and ketones. Georg Thieme Verlag Stuttgart. New York.
Highly selective palladium-catalyzed direct c-h α-monoarylation of carbonyl compounds using water containing the surfactant polyoxyethylene- α-tocopheryl sebacate (PTS) as a solvent
Lessi, Marco,Masini, Tiziana,Nucara, Luca,Bellina, Fabio,Rossi, Renzo
supporting information; experimental part, p. 501 - 507 (2011/04/15)
Highly selective direct C-H α-monoarylation reactions of 4-chromanones, ketones and 2-phenylacetaldehyde with aryl halides have been performed in satisfactory yields by using a tris(dibenzylideneacetone) dipalladium(0)/tri-tert-butylphosphine tetrafluoroborate catalyst system, potassium bicarbonate as the base and a solvent consisting of pure water containing a small amount of polyoxyethylene-α-tocopheryl sebacate (PTS). Analogous reaction conditions have been employed in a tandem process leading to phenyl-substituted isocoumarins from carbonyl compounds and methyl 2-bromobenzoate.
Copper(II) tetrafluroborate-promoted Meinwald rearrangement reactions of epoxides
Robinson, Mathew W.C.,Pillinger, Kathryn S.,Mabbett, Ian,Timms, David A.,Graham, Andrew E.
supporting information; experimental part, p. 8377 - 8382 (2010/11/19)
Epoxides undergo a highly efficient Meinwald rearrangement in the presence of catalytic quantities of copper(II) tetrafluoroborate to give carbonyl compounds in high yields and with excellent selectivity. The low toxicity and ease of handling of this reagent make it an attractive alternative to the more corrosive or costly Lewis acids frequently employed.
Synthesis of enol ethers and enamines by Pd-catalyzed tosylhydrazide- promoted cross-coupling reactions
Barluenga, Jose,Escribano, Maria,Moriel, Patricia,Aznar, Fernando,Valdes, Carlos
supporting information; experimental part, p. 13291-13294+13273 (2010/06/15)
"Chemical Equation Presented" α-Substitution is fine: α-Alkoxycarbonyl and α-aminocarbonyl compounds are good substrates for the recently developed tosylhydrazide-promoted Pd-catalyzed cross-coupling of carbonyls with aryl halides. The reac-tion gives ris
Tuning reactivity and chemoselectivity in electron transfer initiated cyclization reactions: Applications to carbon-carbon bond formation
Seiders II, John R.,Wang, Lijun,Floreancig, Paul E.
, p. 2406 - 2407 (2007/10/03)
In this communication, we demonstrate that the scope of our electron transfer initiated cyclization reaction can be significantly broadened by exploiting the relationship between the oxidation potentials of homobenzylic ethers and the mesolytic benzylic c
