Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions

A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA) as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products.

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Efficient N-formylation of primary aromatic amines using novel solid acid magnetic nanocatalyst

RSC Advances ◽

10.1039/d0ra07476d ◽

2020 ◽

Vol 10 (67) ◽

pp. 41229-41236

Author(s):

Jitendra Kumar Yadav ◽

Priyanka Yadav ◽

Satish K. Awasthi ◽

Alka Agarwal

Keyword(s):

Magnetic Nanoparticles ◽

Aromatic Amines ◽

Sulfonic Acid ◽

Solid Acid ◽

Recyclable Catalyst ◽

Primary Amines ◽

Magnetic Nanocatalyst ◽

Reaction Conditions ◽

Primary Aromatic Amines ◽

First Time

Sulfonic acid functionalized over biguanidine fabricated silica-coated heterogeneous magnetic nanoparticles (NP@SO3H) have been synthesized, well characterized and explored for the first time, as an efficient and recyclable catalyst for N-formylation of primary amines under mild reaction conditions.

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Manganese-mediated reductive functionalization of activated aliphatic acids and primary amines

Nature Communications ◽

10.1038/s41467-020-18834-6 ◽

2020 ◽

Vol 11 (1) ◽

Author(s):

Zhan Li ◽

Ke-Feng Wang ◽

Xin Zhao ◽

Huihui Ti ◽

Xu-Ge Liu ◽

...

Keyword(s):

Carboxylic Acids ◽

Late Stage ◽

Materials Science ◽

Reaction Pathway ◽

Chemical Conversion ◽

Primary Amines ◽

Mechanistic Studies ◽

Reaction Conditions ◽

Aliphatic Acids ◽

Redox Active

Abstract Alkyl carboxylic acids as well as primary amines are ubiquitous in all facets of biological science, pharmaceutical science, chemical science and materials science. By chemical conversion to redox-active esters (RAE) and Katritzky’s N-alkylpyridinium salts, respectively, alkyl carboxylic acids and primary amines serve as ideal starting materials to forge new connections. In this work, a Mn-mediated reductive decarboxylative/deaminative functionalization of activated aliphatic acids and primary amines is disclosed. A series of C-X (X = S, Se, Te, H, P) and C-C bonds are efficiently constructed under simple and mild reaction conditions. The protocol is applicable to the late-stage modification of some structurally complex natural products or drugs. Preliminary mechanistic studies suggest the involvement of radicals in the reaction pathway.

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Efficient synthesis of pyrazolopyridines containing a chromane backbone through domino reaction

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.15.85 ◽

2019 ◽

Vol 15 ◽

pp. 874-880

Author(s):

Razieh Navari ◽

Saeed Balalaie ◽

Saber Mehrparvar ◽

Fatemeh Darvish ◽

Frank Rominger ◽

...

Keyword(s):

Room Temperature ◽

High Selectivity ◽

Domino Reaction ◽

Primary Amines ◽

Efficient Synthesis ◽

Atom Economy ◽

Reaction Conditions ◽

Efficient Approach ◽

Three Component Reaction ◽

High Yields

An efficient approach for the synthesis of pyrazolopyridines containing the aminochromane motif through a base-catalyzed cyclization reaction is reported. The synthesis was carried out through a three-component reaction of (arylhydrazono)methyl-4H-chromen-4-one, malononitrile, primary amines in the presence of Et3N at room temperature. However, carrying out the reaction under the same conditions without base led to a fused chromanyl-cyanopyridine. High selectivity, high atom economy, and good to high yields in addition to mild reaction conditions are the advantages of this approach.

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Synthesis of 2-substituted 5-arylidenethiazolin-4-ones from α,β-unsaturated acyl isothiocyanates

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19810436 ◽

1981 ◽

Vol 46 (2) ◽

pp. 436-445 ◽

Cited By ~ 7

Author(s):

Peter Kutschy ◽

Milan Dzurilla ◽

Pavol Kristian ◽

Kvetoslava Kutschyová

Keyword(s):

Primary Amines ◽

Reaction Conditions ◽

H Nmr ◽

Unsaturated Acyl ◽

Independent Synthesis

α,β-Unsaturated acyl isothiocyanates react with N-methylaniline to give thioureas which, when treated with bromine in chloroform, afford benzothiazoline derivatives. Under the same reaction conditions primary amines, diethylamine, piperidine and morpholine furnish 2-substituted 5-arylidenethiazolin-4-ones. Their structure was corroborated by an independent synthesis and on the basis of spectral (IR, 1H-NMR and mass) evidence.

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Metal-Free Oxidative C(sp3)–N Coupling by HBr and DMSO: A Novel Synthesis of 2,3-Dihydroquinazolin-4(1H)-ones

Synlett ◽

10.1055/s-0036-1591544 ◽

2018 ◽

Vol 29 (07) ◽

pp. 912-917 ◽

Cited By ~ 1

Author(s):

Parviz Ranjbar ◽

Narjes Rezaei ◽

Ehsan Sheikhi

Keyword(s):

Oxidative Cyclization ◽

Cyclization Reaction ◽

Primary Amines ◽

Isatoic Anhydride ◽

Reaction Conditions ◽

Coupling Process ◽

Benzylic Alcohols ◽

Metal Free ◽

Novel Synthesis

A metal-free oxidative C(sp3)–N coupling process has been developed for the synthesis of 2,3-dihydroquinazolin-4(1H)-ones. The reaction between primary amines, isatoic anhydride, and benzylic alcohols in the presence of HBr in DMSO at 80 °C affords 2,3-dihydroquinazolin-4(1H)-ones in excellent yields. Under these reaction conditions, benzylic alcohols react with in situ generated bromodimethylsulfonium bromide to form alkoxysulfonium intermediates. These intermediates undergo an oxidative cyclization reaction with primary amines and isatoic anhydride to produce the title products.

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Nickel-catalyzed C–N bond activation: activated primary amines as alkylating reagents in reductive cross-coupling

Chemical Science ◽

10.1039/c9sc00783k ◽

2019 ◽

Vol 10 (16) ◽

pp. 4430-4435 ◽

Cited By ~ 45

Author(s):

Huifeng Yue ◽

Chen Zhu ◽

Li Shen ◽

Qiuyang Geng ◽

Katharina J. Hock ◽

...

Keyword(s):

Nickel Catalyst ◽

Bond Activation ◽

Cross Coupling ◽

Aryl Halides ◽

Primary Amines ◽

Pyridinium Salts ◽

Reaction Conditions ◽

Alkyl Amines ◽

Alkylating Reagents

The reductive cross coupling of pyridinium salts derived from readily available primary alkyl amines with aryl halides has been achieved under mild reaction conditions using a nickel catalyst.

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Amino-dealkoxylation of hm citruc pectin with n-alkylamines: a kinetic study

Czech Journal of Food Sciences ◽

10.17221/10669-cjfs ◽

2004 ◽

Vol 22 (SI - Chem. Reactions in Foods V) ◽

pp. S235-2S37

Author(s):

L. Sihelniková ◽

A. Synytsya ◽

J. Čopíková

Keyword(s):

Reaction Time ◽

Food Industry ◽

Heterogeneous Reaction ◽

Primary Amines ◽

Reaction Yield ◽

Citrus Pectin ◽

Reaction Conditions ◽

Plant Polysaccharides ◽

Gelling Properties ◽

The Common

Pectins are plant polysaccharides that are widely used in food industry. Chemical modification of pectins influences their technological properties. Amidated pectins are important pectin derivatives with good gelling properties at low-sugar conditions. The common method of pectin amidation is ammonolysis of methyl ester groups of highly methoxylated (HM) pectins in heterogeneous reaction with ammonia in methanol. Aminodealkoxylation (aminolysis) of HM pectin with primary amines leads to the formation of N-alkylpectinamides. The reaction yield of aminolysis depends on reaction time, temperature and the pectin/alkylamine ratio. The reaction of HM citrus pectin (type XSS, Danisco) with five chosen n-alkylamines (n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine and n-octadecylamine) was carried out in N,N-dimethylformamide at 20°C (n-butylamine, n-hexylamine, n-octylamine) and at 50°C (all the amines) for 1–9 days. Obtained results can be applied to prepare N-alkylpectinamides of predicted DA varying the reaction time at the same reaction conditions (temperature, pectin/alkylamine ratio).

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Correction: Exploration of flow reaction conditions using machine-learning for enantioselective organocatalyzed Rauhut–Currier and [3+2] annulation sequence

Chemical Communications ◽

10.1039/d0cc90423f ◽

2020 ◽

Vol 56 (81) ◽

pp. 12256-12256

Author(s):

Masaru Kondo ◽

H. D. P. Wathsala ◽

Makoto Sako ◽

Yutaro Hanatani ◽

Kazunori Ishikawa ◽

...

Keyword(s):

Machine Learning ◽

Reaction Conditions ◽

Flow Reaction

Correction for ‘Exploration of flow reaction conditions using machine-learning for enantioselective organocatalyzed Rauhut–Currier and [3+2] annulation sequence’ by Masaru Kondo et al., Chem. Commun., 2020, 56, 1259–1262, DOI: 10.1039/C9CC08526B.

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