Abstract In this study, the concept of cooperative cation binding catalysis was elegantly applied for direct generation of two contiguous tertiary and quaternary stereogenic centers. Using a highly accessible chiral oligoethylene glycol (oligoEG) as a cation-binding catalyst, asymmetric Mannich reaction of α-thiocyanato cyclic ketones as Mannich donors was performed with α-amido sulfones as the bench-stable imine precursors in the presence of potassium fluoride as the base, affording α-thiocyanato-β-amines possessing tetra-substituted C-SCN centers. The salient features of this process include (a) a transition-metal free and operationally simple procedure, (b) direct use of α- amido sulfones as bench-stable precursors of sensitive imines, …show more content…
In particular, chiral compounds with β-amino-α-thiocyanate moieties are rarely explored in the medicinal chemistry area because of their synthetic difficulty,[5] although they are versatile precursors for the synthesis of β-aminothiols,[6] β-aminosulphonic acids,[7] and 2-iminothiazolidines,[8] present in some stereoselective catalysts, and many biologically and pharmacologically active compounds. To the best of our knowledge, only three related publications have been reported to date.[9,10] In 2013 Sala et al.[10a], and Babu and Parquette[10b] independently reported the asymmetric synthesis of β-amino-α-thiocyanate compounds via the desymmetrization of meso-aziridines with TMSNCS using combined Ca(II)/Mg(II) VAPOL phosphate salts and chiral dimeric yttrium-salen complexes as catalysts. Quite recently, Nakamura et al. also reported the same transformation using chiral imidazoline−phosphoric
8a. No, the product wouldn’t be optically active, since it would contain racemic mixture even though each enantiomer is chiral. Diastereomeric recrystallization can be used to resolve the product into optically active constituents, specifically to produce single enantiomer. (Wikipedia).
The goals in this lab were to have a reaction occur with 4-methylcyclohexanol and an acid catalyst to form our product of 4-methylcyclohexene via an E1 reaction. This reaction is accomplished by removing the –OH group on 4-methylcyclohexanol via dehydration and to have a double bond form via a loss of a hydrogen on a β-Carbon.
In this laboratory experiment a synthesis was performed through several separate steps. The purpose of the experiment was to synthesize tetraphenylcyclopentadienone from benzaldehyde and to run reactions on carbonyl containing compounds. There was a total of three steps that led up to the synthesis of the final product, tetraphenylcyclopentadienone. The first step of the experiment was the condensation of benzaldehyde to yield benzoin. Thiamine catalyst along with water and ethanol were added to the benzaldehyde, then NaOH was added until the solution turned yellow. After recrystallization, the product was benzoin. Step two was the oxidation of benzoin to benzil.
Macromolecules BCM 261 10/13/2014 Caroline Venter 13019865 Introduction Background Many of the molecules that are crucial in living organisms and systems are very large and are usually made up of macromolecules. Macromolecules are organic molecules with a large molecular mass and consist of repeating units called monomers. These repeating monomers are formed via condensation or dehydration reactions (loss of water or other small molecules in order to join two molecules) and usually each have a small molecular mass which contributes to the overall large molecular mass of macromolecules (Jenkins, Kratochvíl, Stepto, & Suter, 2009).
Garner, C., George, C., & Primrose, P. (2017). CHE 3238 Organic Chemistry Laboratory Manual – Baylor University (Fall 2017, Spring and Summer 2018 ed.).
Azacitidine was first synthesized by Piskala and Sorm in 1964 [Piskala A, Sorm F. (1964). Collect Czech Chem. Commun., 29: 2060-2076]. It was developed as a nucleoside antimetabolite specifically used for the treatment of acute myelogenous leukemia (Cihak, 1974;Sorm et al., 1964).
Alantolactone (1): mp 78-79 °C.1H NMR (CDCl3, 500 MHz) δ ppm: 6.06(1H, d, J= 1.8 Hz, H-13a), 5.73(1H, d, J =1.8 Hz, H-13b), 5.26(1H, d, J= 3.9 Hz, H-6), 4.86(1H, m, H-8), 3.64(1H, m, H-7), 2.85(1H, m, H-4), 2.47(1H, d, J=15.5 Hz, H-9a), 2.06(2H, m, H-1a), 1.58(3H, o. m, H-2), 1.54(1H. o. m, H-9b), 1.46(1H, m, H-1b), 1.08(3H, s, 14-CH3), 1.06(1H, d, J= 8.0 Hz, 15-CH3); 13C NMR δppm: 17.01(C-1), 32.99(C-2), 41.98(C-3), 37.87(C-4), 149.45(C-5),119.00(C-6),39.76(C-7), 76.73(C-8), 42.92(C-9), 32.95(C-10), 140.06(C-11), 170.81(C-12), 121.97(C-13), 28.83(C-14), 22.85(C-15). All datas are in correspondence with that reported in the literature [9].
Synthesis of Pentiptycene Butoxy The solid was added with dehydraded K2CO3(150mg, 1.09mmol) and a catalytic amount of 18-crown-6 (5mg) in a dry roundbottom.
Acetaminophen, thiourea, and the three respective ratios were prepared and characterized by ATR FT-IR, PXRD, and DSC analysis.
In 1922, at the University of Illinois, William C. Rose began to research amino acids and its relations to metabolism and nutrition. After years of research, Rose discovered Threonine in 1935. Threonine is one out of three proteinogenic amino acids that have an alcohol group. It is one of the twenty amino acids that are common in animal proteins and needed for regular functioning in humans. It is also considered an essential amino acid because the human body cannot synthesize it from other compounds, therefore, it must be taken with a diet. Threonine is also a hydrophilic molecule, meaning that it is charge-polarized and capable of hydrogen bonding, which enables it to dissolve better in water than in hydrophobic solvents.
With the optimal conditions in hand, various substituted toluenes 1a-k and dialkyl azodicarboxylate 2a-b were applied and a series of corresponding products 3a-n were obtained in 78-90% yields. The results are summarized in Table 2. The reaction of toluene derivatives with neutral and electron-donating substituents such as Me, Et, isPr, N(Me)2 and OMe at the m-, o-, and p- positions on the phenyl ring with diisopropyl diazene-1,2-dicarboxylate/diethyl diazene-1,2-dicarboxylate 2a-b, afforded the corresponding products 3a-j in 78-90% yields (entries 1-10). The toluenes contains strong electron-donating groups OMe and N(Me)2 were Unfavorable substrates for this reaction and gave the desired products in 78% yields (entries 7 and 8), possibly
The recent elucidation of the biosynthetic pathway for stipitatic acid led to the identication of a new FMO (TropB).4 This enzyme catalyses the oxidative dearomatisation of 3-methylorcinaldehyde 1 to produce a dienone 2 (Scheme 1A). This hydroxylation step is remarkably similar to one of the steps reported for the chemical synthesis of azaphilones and their analogues (Scheme 1B).5,6 The synthetic step requires extreme cold temperatures (70 to 10 C), hazardous reagents and relatively long reaction time (30 h). It would be advantageous if related transformations could be performed bio-catalytically using TropB or a related enzyme. This would obviate the utilisation of dangerous chemicals and challenging reaction conditions to facilitate the
Olefin metathesis refers to a reaction involving rearrangement of alkyl groups attached to alkenes through the consecutive cleavage and formation of carbon-carbon double bonds. The reaction is catalysed by a transition metal complex. The existence of such a reaction was hypothesized nearly
A number of synthetic cathinones (aminoketones, ?bath salts?) are tertiary amines containing a cyclic amino group, most commonly pyrrolidine. These totally synthetic compounds can be prepared in a number of regioisomeric designer modification and many of these can yield isomeric major EI-MS fragment ions.
Recently metal-catalyzed carbon–carbon and carbon–heteroatom cross-coupling reactions have been developed as an important reaction class in chemical synthesis.1 Nowadays, there is a variety of competitive methods for synthesis of aryl-nucleophile bonds with various sources of C-, O-, N-, P-, and S-nucleophiles.1-5 Researchers have extensively applied palladium-based catalysts in cross-coupling reactions in both academic and industrial settings,5, 6 however, our goal is the development of a range of copper-based catalysts for cross-coupling reactions. Copper-assisted Sonogashira-type coupling reactions are valuable transformations for organic synthesis. C-C bond formation between aryl halides and terminal aryl- and alkyl-alkynes affords the corresponding substituted internal alkynes. Alkynes are the building blocks of a wide range of pharmaceuticals, natural products, biologically active molecules, conducting polymers, nonlinear, optical and liquid crystal materials.7-12 The routine reaction method for Sonogashira-type coupling is the use of a palladium-based catalyst and a copper(I) salt as a co-catalyst.13 The role of the copper co-catalyst is to produce a copper-acetylide intermediate that subsequently transmetallates to the palladium center.