166823-92-3Relevant academic research and scientific papers
Aldehydes as Alkylating Agents for Ketones
Runikhina, Sofiya A.,Afanasyev, Oleg I.,Biriukov, Klim,Perekalin, Dmitry S.,Klussmann, Martin,Chusov, Denis
, p. 16225 - 16229 (2019)
Common and non-toxic aldehydes are proposed as reagents for alkylation of ketones instead of carcinogenic alkyl halides. The developed reductive alkylation reaction proceeds in the presence of the commercially available ruthenium catalyst [(cymene)RuCl2]2 (as low as 250 ppm) and carbon monoxide as the reducing agent. The reaction works well for a broad substrate scope, including aromatic and aliphatic aldehydes and ketones. It can be carried out without a solvent and often gives nearly quantitative yields of the products. This straightforward and cost-effective method is promising not only for laboratory application but also for industry, which produces carbon monoxide as a large-scale waste product.
Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones
Beltran, Frédéric,Bergamaschi, Enrico,Funes-Ardoiz, Ignacio,Teskey, Christopher J.
supporting information, p. 21176 - 21182 (2020/09/17)
Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
Ni-Catalyzed regio- and stereoselective addition of arylboronic acids to terminal alkynes with a directing group tether
Hari Babu, Madala,Ranjith Kumar, Gadi,Kant, Ruchir,Sridhar Reddy, Maddi
supporting information, p. 3894 - 3897 (2017/04/04)
Addition of arylboronic acids to directing group tethered acetylenes in a regio and stereoselective manner using an inexpensive catalytic system is achieved for the first time to access highly sought after allyl/homoallyl alcohol/amine units. The apparent vinylnickel intermediate was successfully trapped by the Michael electrophiles to get defined tri- and tetra-substituted olefins. An interesting selectivity switch was observed with internal alkynes.
Transition-Metal-Free Synthesis of Homo- and Hetero-1,2,4-Triaryl Benzenes by an Unexpected Base-Promoted Dearylative Pathway
Rehan, Mohammad,Maity, Sanjay,Morya, Lalit Kumar,Pal, Kaushik,Ghorai, Prasanta
, p. 7728 - 7732 (2016/07/07)
An unprecedented approach for the synthesis of homo- and hetero-1,2,4-triaryl benzenes has been developed using a simple base-mediated reaction of either α-aryl cinnamyl alcohols or α,γ-di-aryl propanones. The salient feature of this strategy involves the sequential hydride transfer, regiospecific condensation, regiospecific dearylation, and aromatization under metal-free reaction conditions. The synthesis of unsymmetrically substituted triphenylenes by oxidative coupling of the synthesized 1,2,4-triaryl benzenes has also been demonstrated.
Copper-catalyzed oxidative transformation of secondary alcohols to 1,5-disubstituted tetrazoles
Rokade, Balaji V.,Gadde, Karthik,Prabhu, Kandikere Ramaiah
supporting information, p. 946 - 950 (2014/04/03)
A mild and convenient oxidative transformation of secondary alcohols to 1,5-disubstituted tetrazoles is uncovered by employing trimethylsilyl azide (TMSN3) as a nitrogen source in the presence of a catalytic amount of copper(II) perchlorate hexahydrate [Cu(ClO4)2 .6 H2O] (5 mol%) and 2,3-dichloro-5,6-dicyano-para- benzoquinone (DDQ) (1.2 equiv.) as an oxidant. This reaction is performed under ambient conditions and proceeds through C-C bond cleavage.
Ion pair dynamics: Solvolyses of chiral 1,3-diarylallyl carboxylates as a case study
Troshin, Konstantin,Mayr, Herbert
supporting information, p. 252 - 265 (2013/02/25)
Chiral ion pairs play a key role in modern enantioselective synthesis, though little is known about their properties. We have now used the special features of unsymmetrically substituted allyl derivatives to obtain unprecedented insight into ion pair dynamics. By employing chiral high-performance liquid chromatography, it was possible to follow the time-dependent concentrations of all four isomeric esters (two regioisomeric pairs of enantiomers) and all four isomeric alcohols generated during the hydrolysis of enantiopure 1-(4-chlorophenyl)-3-phenylallyl and 3-(4-chlorophenyl)-1-phenylallyl 4-nitrobenzoates. Combination of these results with the directly measured rate constant for the reaction of the laser-flash photolytically generated 1-(4-chlorophenyl)-3-phenylallyl cation with water provided a complete mechanistic scheme for allyl carboxylate solvolysis. It is demonstrated that solvolysis and internal return can be explained by the same intermediates. The correlation equation log k = sN(N + E) was used to elucidate the variable importance of external and internal return in the solvolysis reactions. This information will be crucial for the interpretation of the ultrafast dynamics of ion pairs generated by femtosecond laser pulses.
Reduction of activated conjugated alkenes by the InCl3-NaBH 4 reagent system
Ranu, Brindaban C.,Samanta, Sampak
, p. 7901 - 7906 (2007/10/03)
A combination of a catalytic amount of indium (III) chloride and sodium borohydride in acetonitrile reduces selectively the carbon-carbon double bonds in conjugated alkenes such as α,α-dicyano olefins, α,β-unsaturated nitriles, cyanoesters, cyanophosphonate and dicarboxylic esters. However, reduction of chalcones is little different. They are reduced to a mixture of saturated ketones and alcohols if the reaction mixture is quenched with H2O, whereas quenching with MeOH leads to saturated alcohols only.
Speedy and regioselective 1,2-reduction of conjugated α,β-unsaturated aldehydes and ketones using NaBH4/I2
Singh, Jasvinder,Kaur, Irvinder,Kaur, Jasamrit,Bhalla, Aman,Kad, Goverdhan L.
, p. 191 - 197 (2007/10/03)
Synthesis of allylic alcohols from α,β-unsaturated aldehydes/ketones has been achieved in excellent yields utilizing NaBH4 and iodine. This reducing agent is mild and tolerant to a number of functional groups.
Vinylogues of Bifonazole: Synthesis and Antifungal Activities
Desideri, Nicoletta,Sestili, Isabella,Artico, Marino,Massa, Silvio,Loi, Anna Giulia,et al.
, p. 431 - 441 (2007/10/03)
Various bifonazole-like derivatives containing styryl or arylbutadienyl groups instead of the 4-biphenylyl moiety were synthesized and tested as antifungal agents. Among the tested derivatives 11c was twice as potent as bifonazole and about 3 times more s
