scholarly journals Synthesis of chiral anti-1,2-diamine derivatives through copper(I)-catalyzed asymmetric α-addition of ketimines to aldimines

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Xu-Cheng Gan ◽  
Cheng-Yuan Zhang ◽  
Feng Zhong ◽  
Ping Tian ◽  
Liang Yin
Keyword(s):  
Nitro Group ◽  
Functional Groups ◽  
Phenyl Group ◽  
Asymmetric Reactions ◽  
Bioactive Molecules ◽  
Sandmeyer Reaction ◽  
Aryl Amine ◽  
Common Structure ◽  
Group A ◽  
High Yields

Abstract Chiral 1,2-diamines serve as not only common structure units in bioactive molecules but also useful ligands for a range of catalytic asymmetric reactions. Here, we report a method to access anti-1,2-diamine derivatives. By means of the electron-withdrawing nature of 2- or 4-nitro-phenyl group, a copper(I)-catalyzed asymmetric α-addition of ketimines derived from trifluoroacetophenone and 2- or 4-NO2-benzylamines to aldimines is achieved, which affords a series of chiral anti-1,2-diamine derivatives in moderate to high yields with moderate to high diastereoselectivity and high to excellent enantioselectivity. Aromatic aldimines, heteroaromatic aldimines, and aliphatic aldimines serve as suitable substrates. The nitro group is demonstrated as a synthetical handle by several transformations, including a particularly interesting Fe(acac)3-catalyzed radical hydroamination with a trisubstituted olefin. Moreover, the aryl amine moiety obtained by the reduction of the nitro group serves as a synthetically versatile group, which leads to the generation of several functional groups by the powerful Sandmeyer reaction, such as -OH, -Br, -CF3, and -BPin.

Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles

2019 ◽  
Author(s):  
Patrick Fier ◽  
Suhong Kim ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Reductive Cleavage ◽  
Bioactive Molecules ◽  
General Method

Sulfonamides are pervasive in drugs and agrochemicals, yet are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react <i>in-situ</i> to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.

scholarly journals Organophotocatalytic selective deuterodehalogenation of aryl or alkyl chlorides

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yanjun Li ◽  
Ziqi Ye ◽  
Yu-Mei Lin ◽  
Yan Liu ◽  
Yumeng Zhang ◽  
...  
Keyword(s):  
Room Temperature ◽  
Sodium Formate ◽  
Bioactive Molecules ◽  
Co Catalyst ◽  
Aryl Chlorides ◽  
Aryl Amine ◽  
Drug Molecules ◽  
Photocatalytic System ◽  
Site Selective ◽  
Environmentally Friendly Method

AbstractDevelopment of practical deuteration reactions is highly valuable for organic synthesis, analytic chemistry and pharmaceutic chemistry. Deuterodehalogenation of organic chlorides tends to be an attractive strategy but remains a challenging task. We here develop a photocatalytic system consisting of an aryl-amine photocatalyst and a disulfide co-catalyst in the presence of sodium formate as an electron and hydrogen donor. Accordingly, many aryl chlorides, alkyl chlorides, and other halides are converted to deuterated products at room temperature in air (>90 examples, up to 99% D-incorporation). The mechanistic studies reveal that the aryl amine serves as reducing photoredox catalyst to initiate cleavage of the C-Cl bond, at the same time as energy transfer catalyst to induce homolysis of the disulfide for consequent deuterium transfer process. This economic and environmentally-friendly method can be used for site-selective D-labeling of a number of bioactive molecules and direct H/D exchange of some drug molecules.

Preparation of Functionalized Diorganomagnesium Reagents in Toluene via Bromine or Iodine/Magnesium-Exchange Reactions

Synthesis ◽  
2021 ◽  
Author(s):  
Alexandre Desaintjean ◽  
Fanny Danton ◽  
Paul Knochel
Keyword(s):  
Exchange Reaction ◽  
Nitro Group ◽  
General Formula ◽  
Functional Groups ◽  
Exchange Reactions ◽  
Acyl Chlorides ◽  
Aryl Iodides ◽  
Highly Sensitive ◽  
Wide Range ◽  
Magnesium Exchange

A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents were prepared in toluene within 10 to 120 min between −78 °C and 25 °C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as a triazene or a nitro group, were tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arenes and alkenes derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.

Products of reaction between styrene and some radicals with 2,2-diphenyl-1-picrylhydrazyl

1981 ◽  
Vol 59 (21) ◽  
pp. 3095-3104 ◽  
Author(s):  
Karl R. Kopecky ◽  
Michael C. Hall
Keyword(s):  
Nitro Group ◽  
Considerable Increase ◽  
Phenyl Group ◽  
Diels Alder ◽  
Benzyl Radicals ◽  
Products Of Reaction ◽  
Cis And Trans

Addition of 2,2-diphenyl-1-picrylhydrazyl DPPH to styrene at 75 °C results in little change in the amounts of cis- and trans-1,2-diphenylcyclobutane and 1,2,3,4-tetrahydro-1-phenylnaphthalene, in a slightly smaller amount of 1-phenylnaphthalene, and in a considerable increase in the amount of 1,2-dihydro-1-phenylnaphthalene that are formed. Formation of the styrene trimer 1,2,3,4-tetrahydro-1-phenyl-4-(1-phenylethyl)naphthalene is eliminated completely. Products derived from DPPH are l-(4-nitro-phenyl)-1-phenyl-2-picrylhydrazine 9 and 1-[2,6-dinitro-4-(1,2,3,4-tetrahydro-4-phenyl-1-naphthyl)phenyl]-2,2-diphenylhydrazine, 10. DPPH intercepts the thermally formed Diels–Alder dimer of styrene as soon as it is formed to give the 1,2,3,4-tetrahydro-4-phenyl-1-naphthyl radical.Thermolysis of bis(1,2,3,4-tetrahydro-4-phenyl-1-naphthyl)diazene in the presence of DPPH yields 20% of 10, 10,% of l-[2,6-dinitro-4-(1,2,3,4-tetrahydro-4-phenyl-1-naphthyl)phenyl]-2-(4-nitrophenyl)-2-phenylhydrazine and 9 while thermolysis of 1,2-bis(1-phenylethyl)diazene in the presence of DPPH yields 9 and 44% of 1-[2,6-dinitro-4-(1-phenylethyl)phenyl]-2,2-diphenyl-hydrazine showing that substituted benzyl radicals efficiently displace the 4-nitro group of DPPH. The nitro group is transferred to an unsubstituted phenyl group of DPPH.

scholarly journals Cinnamic Acid Derivatives as α-Glucosidase Inhibitor Agents

2017 ◽  
Vol 17 (1) ◽  
pp. 151 ◽  
Author(s):  
Teni Ernawati ◽  
Maksum Radji ◽  
Muhammad Hanafi ◽  
Abdul Mun’im ◽  
Arry Yanuar
Keyword(s):  
Functional Groups ◽  
Cinnamic Acid ◽  
Phenyl Group ◽  
Chemical Compounds ◽  
Cinnamic Acid Derivative ◽  
Cinnamic Acid Derivatives ◽  
Glucosidase Inhibitor ◽  
Glucosidase Inhibitors ◽  
Derivatives Of ◽  
Additive Reaction

This paper reviews biological activity of some cinnamic acid derivative compounds which are isolated from natural materials and synthesized from the chemical compounds as an agent of α-glucosidase inhibitors for the antidiabetic drug. Aegeline, anhydroaegeline and aeglinoside B are natural products isolated compounds that have potential as an α-glucosidase inhibitor. Meanwhile, α-glucosidase inhibitor class of derivatives of cinnamic acid synthesized compounds are p-methoxy cinnamic acid and p-methoxyethyl cinnamate. Chemically, cinnamic acid has three main functional groups: first is the substitution of the phenyl group, second is the additive reaction into the α-β unsaturated, and third is the chemical reaction with carboxylic acid functional groups. The synthesis and modification of the structure of cinnamic acid are very influential in inhibitory activity against α-glucosidase.

Alkyl Carbagermatrane Enabled Synthesis of Seven-Membered Carbocycle-Fused Aromatics through Catellani Strategy

Synthesis ◽  
2021 ◽  
Author(s):  
Xiu-Ying Xie ◽  
Wei-Tao Jiang ◽  
Bin Xiao
Keyword(s):  
Natural Product ◽  
Functional Groups ◽  
Bioactive Molecules ◽  
Intermolecular Cyclization

Synthesis of seven-membered carbocycle-fused aromatics was realized by Catellani reaction using terminally brominated alkyl carbagermatranes through intermolecular cyclization manner. Various functional groups were well tolerated, and this transformation was also expanded to the synthesis of carbocycles of other size. The utility of this method was demonstrated by modification of natural product derivatives and synthesis of bioactive molecules.

A SERIES OF MODEL COMPOUNDS FOR THE STUDY OF AROMATIC REACTIONS

1965 ◽  
Vol 43 (2) ◽  
pp. 337-342
Author(s):  
S. Safe ◽  
R. Y. Moir
Keyword(s):  
Nitro Group ◽  
Systematic Variation ◽  
Model Compounds ◽  
Group A ◽  
Methylene Group

A series of halogenated phthalides was prepared in which there was a systematic variation in the identity, position, and degree of activation of the halogen, and in the activation of the methylene group. A study was made of the selective reductive removal of halogen in the presence of another halogen, or of a nitro group.

scholarly journals Recent Progress in Nitro-Promoted Direct Functionalization of Pyridones and Quinolones

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 673 ◽  
Author(s):  
Feiyue Hao ◽  
Nagatoshi Nishiwaki
Keyword(s):  
Nitro Group ◽  
Functional Groups ◽  
Recent Progress ◽  
Alder Reaction ◽  
Diels Alder ◽  
Organic Syntheses ◽  
Diels Alder Reaction ◽  
Direct Functionalization ◽  
Nucleophilic Reagents

Nitro group is one of the most important functional groups in organic syntheses because its strongly electron-withdrawing ability activates the scaffold, facilitating the reaction with nucleophilic reagents or the Diels–Alder reaction. In this review, recent progress in the nitro-promoted direct functionalization of pyridones and quinolones is highlighted to complement previous reviews.

Synthesis of α,β-Unsaturated Phosphine Sulfides

Synthesis ◽  
2019 ◽  
Vol 52 (01) ◽  
pp. 141-149 ◽  
Author(s):  
Xian-Liang Wang ◽  
Jin-Xiang Chen ◽  
Xue-Shun Jia ◽  
Liang Yin
Keyword(s):  
Functional Groups ◽  
Nucleophilic Addition ◽  
Asymmetric Reactions ◽  
Phosphine Oxides ◽  
Lawesson’S Reagent ◽  
Lawesson's Reagent ◽  
New Applications

α,β-Unsaturated phosphine sulfides may exhibit different reactivity from α,β-unsaturated phosphine oxides toward nucleophilic addition and thus may find new applications in copper(I)-catalyzed asymmetric reactions. Herein, various α,β-unsaturated phosphine sulfides were prepared in moderate to excellent yields from the parent α,β-unsaturated phosphine oxides with Lawesson’s reagent. The reaction enjoys a broad substrate scope and tolerates a variety of functional groups.

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