scholarly journals One-pot, modular approach to functionalized ketones via nucleophilic addition/Buchwald–Hartwig amination strategy

2019 ◽  
Vol 55 (20) ◽  
pp. 2908-2911 ◽  
Author(s):  
Jorn de Jong ◽  
Dorus Heijnen ◽  
Hugo Helbert ◽  
Ben L. Feringa
Keyword(s):  
Nucleophilic Addition ◽  
Modular Approach ◽  
One Pot ◽  
Lithium Amides ◽  
Organolithium Reagents

A one-pot procedure for 1,2-addition of organolithium reagents to amides followed by Buchwald–Hartwig amination with in situ released lithium amides is presented.

One-Pot, Modular Approach to Functionalized Ketones via Nucleophilic Addition of Alkyllithium Reagents to Benzamides and Pd-Catalyzed α-Arylation

ACS Catalysis ◽  
2016 ◽  
Vol 6 (4) ◽  
pp. 2622-2625 ◽  
Author(s):  
Alexander T. Wolters ◽  
Valentin Hornillos ◽  
Dorus Heijnen ◽  
Massimo Giannerini ◽  
Ben L. Feringa
Keyword(s):  
Nucleophilic Addition ◽  
Modular Approach ◽  
One Pot

Aminolithiation of carbon-carbon double bonds as a powerful tool in organic synthesis

2009 ◽  
Vol 81 (2) ◽  
pp. 247-253 ◽  
Author(s):  
Kiyoshi Tomioka ◽  
Takeo Sakai ◽  
Tokutaro Ogata ◽  
Yasutomo Yamamoto
Keyword(s):  
Carbonyl Compounds ◽  
Chiral Ligand ◽  
Powerful Method ◽  
Double Bonds ◽  
One Pot ◽  
Bond Forming ◽  
Lithium Amides ◽  
Lithium Enolates ◽  
Amination Product

A conjugate amination of α,β-unsaturated carbonyl compounds with lithium amides has become a powerful method of N-C bond-forming reactions. Chiral ligand-controlled asymmetric version of the conjugate amination of enoates was developed for practical bench chemistry, giving the enantioenriched amination product with over 99 % ee. In situ diastereoselective alkylation of resulting lithium enolates allowed us to form vicinal N-C and C-C bonds in a one-pot operation. This protocol enabled us to realize a short-step asymmetric synthesis of otamixaban key intermediate. Treatment of product 3-benzylamino- and 3-allylaminoesters with tert-butyllithium gave five- or seven-membered lactams through [1,2]- or [2,3]-rearrangement of intermediate β-lactams. Isolated C-C double bonds were also found to accept intramolecular aminolithiation affording the corresponding hydroamination products. Chiral lithiophilic ligand-catalyzed reaction gave enantioenriched hydroamination products with high ee. Stereoselective intramolecular aminolithiation of allylaminoalkenes was coupled with subsequent carbolithiation to give doubly cyclized product amines.

scholarly journals One-pot synthesis of GABA amides via the nucleophilic addition of amines to 3,3-disubstituted cyclopropenes

2015 ◽  
Vol 13 (34) ◽  
pp. 8993-8995 ◽  
Author(s):  
Vladimir A. Maslivetc ◽  
Marina Rubina ◽  
Michael Rubin
Keyword(s):  
Double Bond ◽  
Nucleophilic Addition ◽  
Ring Opening ◽  
Secondary Amines ◽  
One Pot ◽  
One Pot Synthesis ◽  
Primary And Secondary Amines ◽  
Donor Acceptor

A one-pot synthesis of various GABA amides has been demostrated, employing the nucleophilic addition of primary and secondary amines across the double bond of cyclopropene-3-carboxamides, followed by ring-opening of the resulting donor–acceptor cyclopropanes and subsequent in situ reduction of enamine intermediates.

A Revised Modular Approach to D8-THC and Derivatives Through Late-Stage Suzuki-Miyaura Cross-Coupling Reactions

2019 ◽  
Author(s):  
Victor Bloemendal ◽  
Floris P. J. T. Rutjes ◽  
Thomas J. Boltje ◽  
Daan Sondag ◽  
Hidde Elferink ◽  
...  
Keyword(s):  
Biological Activity ◽  
Late Stage ◽  
Medicinal Chemistry ◽  
Cross Coupling ◽  
Modular Approach ◽  
Coupling Reactions ◽  
One Pot ◽  
Biologically Relevant ◽  
Cross Coupling Reactions ◽  
Chemistry Research

<p>In this manuscript we describe a modular pathway to synthesize biologically relevant (–)-<i>trans</i>-Δ<sup>8</sup>-THC derivatives, which can be used to modulate the pharmacologically important CB<sub>1</sub> and CB<sub>2</sub> receptors. This pathway involves a one-pot Friedel-Crafts alkylation/cyclization protocol, followed by Suzuki-Miyaura cross-coupling reactions and gives rise to a series of new Δ<sup>8</sup>-THC derivatives. In addition, we demonstrate using extensive NMR evidence that similar halide-substituted Friedel-Crafts alkylation/cyclization products in previous articles were wrongly assigned as the para-isomers, which also has consequence for the assignment of the subsequent cross-coupled products and interpretation of their biological activity. </p> <p>Considering the importance of the availability of THC derivatives in medicinal chemistry research and the fact that previously synthesized compounds were wrongly assigned, we feel this research is describing a straightforward pathway into new cannabinoids.</p>

The Total Synthesis of Rhabdastrellic Acid A

2018 ◽  
Author(s):  
Yaroslav Boyko ◽  
Christopher Huck ◽  
David Sarlah
Keyword(s):  
Total Synthesis ◽  
Late Stage ◽  
Cross Coupling ◽  
Side Chains ◽  
General Strategy ◽  
Modular Approach ◽  
Linear Sequence ◽  
Generating Sequence ◽  
First Time

<div>The first total synthesis of rhabdastrellic acid A, a highly cytotoxic isomalabaricane triterpenoid, has been accomplished in a linear sequence of 14 steps from commercial geranylacetone. The prominently strained <i>trans-syn-trans</i>-perhydrobenz[<i>e</i>]indene core characteristic of the isomalabaricanes is efficiently accessed in a selective manner for the first time through a rapid, complexity-generating sequence incorporating a reductive radical polyene cyclization, an unprecedented oxidative Rautenstrauch cycloisomerization, and umpolung 𝛼-substitution of a <i>p</i>-toluenesulfonylhydrazone with in situ reductive transposition. A late-stage cross-coupling in concert with a modular approach to polyunsaturated side chains renders this a general strategy for the synthesis of numerous family members of these synthetically challenging and hitherto inaccessible marine triterpenoids.</div>

Indium Bromide-catalyzed Unprecedented Hydrogenolysis: A Novel One-Pot Synthesis of Per-O-Acetylated β-carboxymethyl O and S-glycosides

2020 ◽  
Vol 24 (8) ◽  
pp. 900-908
Author(s):  
Ram Naresh Yadav ◽  
Amrendra K Singh ◽  
Bimal Banik
Keyword(s):  
Asymmetric Synthesis ◽  
Chiral Auxiliary ◽  
Bioactive Molecules ◽  
One Pot ◽  
Enantiomerically Pure ◽  
Stereoselective Glycosylation ◽  
One Pot Synthesis ◽  
Wide Range

Numerous O (oxa)- and S (thia)-glycosyl esters and their analogous glycosyl acids have been accomplished through stereoselective glycosylation of various peracetylated bromo sugar with benzyl glycolate using InBr3 as a glycosyl promotor followed by in situ hydrogenolysis of resulting glycosyl ester. A tandem glycosylating and hydrogenolytic activity of InBr3 has been successfully investigated in a one-pot procedure. The resulting synthetically valuable and virtually unexplored class of β-CMGL (glycosyl acids) could serve as an excellent potential chiral auxiliary in the asymmetric synthesis of a wide range of enantiomerically pure medicinally prevalent β-lactams and other bioactive molecules of diverse medicinal interest.

scholarly journals NIR responsive tumor vaccine in situ for photothermal ablation and chemotherapy to trigger robust antitumor immune responses

2021 ◽  
Vol 19 (1) ◽  
Author(s):  
Lirong Zhang ◽  
Jingjing Zhang ◽  
Lixia Xu ◽  
Zijian Zhuang ◽  
Jingjin Liu ◽  
...  
Keyword(s):  
Immune Responses ◽  
Tumor Vaccine ◽  
Oxidative Polymerization ◽  
Delivery Mode ◽  
Tumor Treatment ◽  
One Pot ◽  
Photothermal Ablation ◽  
Prolonged Retention ◽  
The One

Abstract Background Therapeutic tumor vaccine (TTV) that induces tumor-specific immunity has enormous potentials in tumor treatment, but high heterogeneity and poor immunogenicity of tumor seriously impair its clinical efficacy. Herein, a novel NIR responsive tumor vaccine in situ (HA-PDA@IQ/DOX HG) was prepared by integrating hyaluronic acid functionalized polydopamine nanoparticles (HA-PDA NPs) with immune adjuvants (Imiquimod, IQ) and doxorubicin (DOX) into thermal-sensitive hydrogel. Results HA-PDA@IQ NPs with high photothermal conversion efficiency (41.2%) and T1-relaxation efficiency were using HA as stabilizer by the one-pot oxidative polymerization. Then, HA-PDA@IQ loaded DOX via π-π stacking and mixed with thermal-sensitive hydrogel to form the HA-PDA@IQ/DOX HG. The hydrogel-confined delivery mode endowed HA-PDA@IQ/DOX NPs with multiple photothermal ablation performance once injection upon NIR irradiation due to the prolonged retention in tumor site. More importantly, this mode enabled HA-PDA@IQ/DOX NPs to promote the DC maturation, memory T cells in lymphatic node as well as cytotoxic T lymphocytes in spleen. Conclusion Taken together, the HA-PDA@IQ/DOX HG could be served as a theranostic tumor vaccine for complete photothermal ablation to trigger robust antitumor immune responses.

Regioselective Functionalization of N-Fused Heteroaromatics via FeCl3-Catalyzed Nucleophilic Addition to Activated N-Heterocycles

Synthesis ◽  
2020 ◽  
Author(s):  
Ikyon Kim ◽  
Sung June Kim ◽  
Sunhee Lee
Keyword(s):  
Aromatic Compounds ◽  
Nucleophilic Addition ◽  
Chemical Space ◽  
Wide Range ◽  
Regioselective Functionalization

AbstractBroadening of nitrogen-fused heteroaromatic chemical space such as indolizine and pyrrolo[1,2-a]pyrazine was achieved via FeCl­3-catalyzed nucleophilic addition of these N-fused aromatic compounds to a wide range of azolinium systems generated in situ, leading to novel N-fused heteroaromatic scaffolds with dearomatized N-heterocyclic substituents regioselectively. Nucleophilic addition of indolizines and pyrrolo[1,2-a]pyrazines mainly occurred at the C1 position of the isoquinoliniums and at the C4 site of the quinoliniums.

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