Reaction of α,β-alkynylketones with β-amino alcohols: pseudoephedrine- assisted cleavage of triple bond via formal internal redox process

Vasilevsky, S. F.; Davydova, Maria P.; Mamatuyk, Victor I.; Pleshkova, N. V.; Fadeev, Dmitry S.; Alabugin, Igor V.

doi:10.1016/j.mencom.2015.09.021

Cited by 7 publications

(6 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, when the same reaction was performed with EtONa, which was obtained from ethanol that contained a small amount of water, only 4‐methoxyphenylacetylene 5 was isolated in good yield. The similar cleavage of acetylenic ketones by using nitrogen nucleophiles has been recently reported …”

Section: Resultssupporting

confidence: 65%

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones

et al. 2017

View full text Add to dashboard Cite

A highly efficient synthetic method for the preparation of of 6‐trifluoromethylated pyrimidines was developed. The reaction of CF3‐substituted ynones and nitrogen 1,3‐bis(nucleophile)s was employed for the one‐pot assembly of the pyrimidine core. The cascade route proceeded through an aza‐Michael addition, intramolecular cyclization, and dehydration reaction sequence to give the target heterocycles in excellent yields (up to 97 %). When acetamidine was used as the bis(nucleophile), the unexpected addition of two equivalents of the CF3‐substituted ynone to the acetamidine was observed.

show abstract

Section: Resultssupporting

confidence: 65%

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Some reactions have been performed at room temperature, 102,350,355,356 but higher temperatures are more common, 141,184,357−360 even as high as 120 °C150,361 and 140 °C, 362 and typically with 1.0−1.1 molar eq of the amine and no additional reagent(s), although the amine has also been used as solvent. 14,174,244,353,354 A variety of solvents have been applied, including alcohols 149,350,358 and nonprotic solvents like PhMe, 182,150 MeCN, 363 DCM, THF, 139,141 DMSO, 364,365 1,4dioxane, 151,366 and DMF. 367 The reaction time is usually short, but when anilines with one or several electron-withdrawing groups attached to the ring are used, even days have been required to obtain some product.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…360 Hydroxylated amines give the expected enaminones in good to excellent yields when performed under mild conditions (EtOH, rt) 349,350,355 and in refluxing dioxane. 366 The reaction is stereoselective and give the Z isomers exclusively when primary amines are used, but subsequent cyclization via hemiacetal formation followed by an elimination has not been reported. However, the stability at elevated temperature may be limited.…”

Section: Conjugate Additionsmentioning

confidence: 99%

“…355 And when a sterically hindered ethanolamine like pseudoephedrine is reacted with some 3-aryl-1-(3,4,5-trimethoxyphenyl)prop-2-en-1-one derivatives in refluxing dioxane that is not absolutely dry, decomposition takes place. 366 Intermolecular hydroamination of conjugated ynones followed by cyclization has been applied by Langer and co-workers to synthesize aminoquinolones. 152 The substrates were four 2chloro-5-nitrophenyl 1-alkynyl ketones 150, which suffered Michael addition and formation of enaminones 340 when treated with primary amines at elevated temperature.…”

Section: Conjugate Additionsmentioning

confidence: 99%

See 1 more Smart Citation

Conjugated Ynones in Organic Synthesis

2019

View full text Add to dashboard Cite

This review article will consider the preparation and application of ynones in synthetic organic chemistry. Concerning the preparation of these bifunctional compounds, several methodologies starting from propargyl alcohols, acyl derivatives, both by using alkynylmetal reagents or by transition metal (mainly palladium and copper) catalyzed alkynylations, carbon monoxide (carbonylation of terminal alkynes and alkenes), and other substrates will be discussed. The reactivity and synthetic applications of ynones will be focused on conjugate additions with boron-, carbon-, nitrogen-, oxygen-, and other heteroatom-containing nucleophiles, as well as radicals. Then, cycloaddition processes will include [2 + 2] cycloadditions, [3 + 2] 1,3-dipolar cycloadditions (with azides, nitrones, azomethine imines and ylides, nitrile oxides, diazo compounds, and other dipoles), and [4 + 2] cycloadditions (mainly Diels–Alder-type reactions). The reduction of the triple bond, addition to the carbonyl group (using carbon- and heteronucleophiles and reductions), and other not so commonly used processes (such as aldol reactions, cyclizations, and isomerizations) will be considered at the end.

show abstract

“…Reactions of α -alkynylketones with other type of binucleophiles, aminoalcohols, proceed in a more complex manner [127]. The effects of electronic and steric factors were investigated by choosing substrates containing donor ( p -methoxyphenyl) and acceptor (phenyl and p -nitrophenyl) substituents.…”

Section: Alkynes As Carbonyl Surrogates In the Synthesis Of Aldol mentioning

confidence: 99%

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

et al. 2019

View full text Add to dashboard Cite

The high energy packed in alkyne functional group makes alkyne reactions highly thermodynamically favorable and generally irreversible. Furthermore, the presence of two orthogonal π-bonds that can be manipulated separately enables flexible synthetic cascades stemming from alkynes. Behind these “obvious” traits, there are other more subtle, often concealed aspects of this functional group’s appeal. This review is focused on yet another interesting but underappreciated alkyne feature: the fact that the CC alkyne unit has the same oxidation state as the -CH2C(O)- unit of a typical carbonyl compound. Thus, “classic carbonyl chemistry” can be accessed through alkynes, and new transformations can be engineered by unmasking the hidden carbonyl nature of alkynes. The goal of this review is to illustrate the advantages of using alkynes as an entry point to carbonyl reactions while highlighting reports from the literature where, sometimes without full appreciation, the concept of using alkynes as a hidden entry into carbonyl chemistry has been applied.

show abstract

Reaction of α,β-alkynylketones with β-amino alcohols: pseudoephedrine- assisted cleavage of triple bond via formal internal redox process

Cited by 7 publications

References 11 publications

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones

Conjugated Ynones in Organic Synthesis

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Contact Info

Product

Resources

About

Reaction of α,β-alkynylketones with β-amino alcohols: pseudoephedrine- assisted cleavage of triple bond via formal internal redox process

Cited by 7 publications

References 11 publications

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF3‐Ynones

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF3‐Ynones

Conjugated Ynones in Organic Synthesis

Alkynes as Synthetic Equivalents of Ketones and Aldehydes: A Hidden Entry into Carbonyl Chemistry

Contact Info

Product

Resources

About

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones

One‐Pot, Atom and Step Economy (PASE) Assembly of Trifluoromethylated Pyrimidines from CF₃‐Ynones