Recent Advances in the Synthesis of Enantiomerically Enriched Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols through Addition of Organometallic Reagents to Carbonyl Compounds

Synthesis ◽  
2020 ◽  
Vol 52 (13) ◽  
pp. 1855-1873
Author(s):  
Senthil Narayanaperumal ◽  
Ricardo S. Schwab ◽  
Wystan K. O. Teixeira ◽  
Danilo Yano de Albuquerque
Keyword(s):  
Carbonyl Compounds ◽  
Building Blocks ◽  
Short Review ◽  
Biological Properties ◽  
Enantioselective Synthesis ◽  
Grignard Reagents ◽  
Organometallic Reagents ◽  
Important Family ◽  
Organolithium Reagents ◽  
Organozinc Reagents

Enantiomerically enriched diaryl, aryl heteroaryl, and dihetero­aryl alcohols are an important family of compounds known for their biological properties. Moreover, these molecules are highly privileged scaffolds used as building blocks for the synthesis of pharmaceutically relevant products. This short review provides background on the enantioselective arylation and heteroarylation of carbonyl compounds, as well as, the most significant improvements in this field with special emphasis on the application of organometallic reagents.1 Introduction2 Background on the Enantioselective Synthesis of Diaryl, Aryl Heteroaryl, and Diheteroaryl Alcohols3 Organozinc Reagents4 Organolithium Reagents5 Grignard Reagents6 Organoaluminum Reagents7 Organotitanium Reagents8 Organobismuth Reagents9 Miscellaneous10 Conclusion

scholarly journals Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

2008 ◽  
Vol 80 (5) ◽  
pp. 1025-1037 ◽  
Author(s):  
Koen Geurts ◽  
Stephen P. Fletcher ◽  
Anthoni W. van Zijl ◽  
Adriaan J. Minnaard ◽  
Ben L. Feringa
Keyword(s):  
Building Blocks ◽  
Field Work ◽  
Grignard Reagents ◽  
Allylic Alcohols ◽  
Substitution Reactions ◽  
Organometallic Reagents ◽  
Bond Forming ◽  
Allylic Alkylations ◽  
Ferrocenyl Ligands ◽  
High Yields

Asymmetric allylic alkylations (AAAs) are among the most powerful C-C bond-forming reactions. We present a brief overview of copper-catalyzed AAAs with organometallic reagents and discuss our own contributions to this field. Work with zinc reagents and phosphoramidite ligands provided a framework for later developments which employ Grignard reagents and ferrocenyl ligands. High yields and excellent regioselectivities and enantioselectivities are achieved. The AAAs may be more general than previously envisioned, in terms of using substrates functionalized with heteroatoms at various positions; heteroatom substituents at the γ-position provide densely functionalized building blocks. These h-AAA reactions rely on the design of appropriate substrates containing heteroatoms and have allowed us to demonstrate viable new approaches toward the synthesis of versatile organic building blocks. We illustrate that the chiral secondary allylic alcohols, primary homo-allylic alcohols and amines can readily be obtained in high enantiomeric purity in a catalytic asymmetric fashion by copper-catalyzed AAAs. Furthermore, we show that manipulation of the terminal olefin provides chiral building blocks where the ee of the starting materials is preserved.

Recent Application of Chiral Aryliodine Based on the 2-Iodo­resorcinol Core in Asymmetric Catalysis

Synthesis ◽  
2020 ◽  
Author(s):  
Yang Wang ◽  
Zheng-Guang Wu ◽  
Bing Yang ◽  
Xin-Xing Wu
Keyword(s):  
Asymmetric Catalysis ◽  
Carbonyl Compounds ◽  
Short Review ◽  
Enantioselective Synthesis ◽  
Hypervalent Iodine ◽  
Side Chains ◽  
Recent Application ◽  
Asymmetric Oxidation ◽  
Phenol Compounds ◽  
Phenol Derivatives

AbstractChiral iodoarenes have been steadily increasing in importance in recent years, especially in enantioselective synthesis and catalysis. Since the development of the concept of chiral iodine(I/III) catalysis, the use of various chiral aryliodine frameworks has been explored in this area. This short review gives an overview of the use of chiral hypervalent iodine(I/III) reagents based on the 2-iodoresorcinol core with two attached two lactic side chains bearing ester or amide groups for the catalytic enantioselective dearomatization of phenol compounds, asymmetric oxidation of alkenes, and enantioselective α-functionalization of carbonyl compounds highlighting the excellent reactivities in terms of yield and enantioselectivity.1 Introduction2 Enantioselective Dearomatization of Phenol Derivatives3 Asymmetric Oxidation of Alkenes4 Enantioselective α-Functionalization of Carbonyl Compounds5 Conclusion and Outlook

Directed, Palladium(II)-Catalyzed Enantioselective anti-Carboboration of Alkenyl Carbonyl Compounds

2019 ◽  
Author(s):  
Zhen Liu ◽  
Xiaohan Li ◽  
Tian Zeng ◽  
Keary Engle
Keyword(s):  
Carbonyl Compounds ◽  
Building Blocks ◽  
New Method ◽  
Carbon Based

A substrate-directed enantioselective <i>anti</i>-carboboration reaction of alkenes has been developed, wherein a carbon based nucleophile and a boron moiety are installed across the C=C bond through a 5- or 6-membered palladacycle intermediate. The reaction is promoted by a palladium(II) catalyst and a mondentate oxzazoline ligand. A range of enantioenriched secondary alkylboronate products were obtained with moderate to high enantioselectivity that could be further upgraded by recrystallization. This work represents a new method to synthesize versatile and valuable alkylboronate building blocks. Building on an earlier mechanistic proposal by Peng, He, and Chen, a revised model is proposed to account for the stereoconvergent nature of this transformation.

Modular, Stereocontrolled Cβ–H/Cα–C Activation of Alkyl Carboxylic Acids

2019 ◽  
Author(s):  
Ming Shang ◽  
Karla S. Feu ◽  
Julien C. Vantourout ◽  
Lisa M. Barton ◽  
Heather L. Osswald ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Heterocyclic Compounds ◽  
Cross Coupling ◽  
Building Blocks ◽  
Enantioselective Synthesis ◽  
Carbon Centers ◽  
Drug Candidates ◽  
Rapid Diversification ◽  
Directing Group ◽  
Compound Series

<div> <div> <div> <p>The union of two powerful transformations, directed C–H activation and decarboxylative cross-coupling, for the enantioselective synthesis of vicinally functionalized alkyl, carbocyclic, and heterocyclic compounds is described. Starting from simple carboxylic acid building blocks, this modular sequence exploits the residual directing group to access more than 50 scaffolds that would be otherwise extremely difficult to prepare. The tactical use of these two transformations accomplishes a formal vicinal difunctionalization of carbon centers in a way that is modular and thus amenable to rapid diversity incorporation. A simplification of routes to known preclinical drug candidates is presented along with the rapid diversification of an antimalarial compound series. </p> </div> </div> </div>

scholarly journals Core-Substituted Naphthalene-diimides (cNDI) and Related Derivatives: Versatile Scaffold for Supramolecular Assembly and Functional Materials

2021 ◽  
Author(s):  
Anurag Mukherjee ◽  
Suhrit Ghosh
Keyword(s):  
Photophysical Properties ◽  
Supramolecular Assembly ◽  
Functional Materials ◽  
Building Blocks ◽  
Short Review ◽  
Molecular Engineering ◽  
Organic Optoelectronics ◽  
Naphthalene Diimide ◽  
Naphthalene Diimides ◽  
Derivatives Of

Naphthalene-diimide (NDI) derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional material. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules.

Enantioselective Synthesis of O-Methoxycarbonyl Cyanohydrins: Chiral Building Blocks Generated by Bifunctional Catalysis with BINOLAM-AlCl.

ChemInform ◽  
2006 ◽  
Vol 37 (33) ◽  
Author(s):  
Alejandro Baeza ◽  
Jesus Casas ◽  
Carmen Najera ◽  
Jose M. Sansano ◽  
Jose M. Saa
Keyword(s):  
Building Blocks ◽  
Enantioselective Synthesis ◽  
Bifunctional Catalysis

Application of α-Amino Radicals as the Reaction Activators

Synthesis ◽  
2021 ◽  
Author(s):  
Yong-liang Su ◽  
Michael P. Doyle
Keyword(s):  
Halogen Atom ◽  
Building Blocks ◽  
Short Review ◽  
Single Electron ◽  
Radical Species ◽  
Sulfonium Salts ◽  
Radical Intermediates ◽  
Organic Halides

α-Aminoalkyl radicals are easily accessible through multiple pathways from various precursors. Apart from their utilization as N-containing building blocks, they have recently been used as halogen atom abstraction reagents or single-electron reductants to transform organic halides or sulfonium salts to their corresponding highly reactive radical species. Benefiting from the richness of various halides and the diverse reactivity of radical intermediates, new transformations of halides and sulfonium salts have been developed. This short review summarizes this emerging chemistry that uses α-amino radicals as the reaction activators.

scholarly journals Technetium-99m nitrido radiopharmaceuticals with unprecedented biological properties

2002 ◽  
Vol 45 (spe) ◽  
pp. 135-142 ◽  
Author(s):  
Adriano Duatti ◽  
Alessandra Boschi ◽  
Licia Uccelli
Keyword(s):  
Perfusion Imaging ◽  
Short Review ◽  
Biological Properties ◽  
Biological Evaluation ◽  
Chemical Methods ◽  
Efficient Tool ◽  
Technetium 99M ◽  
Heart Perfusion ◽  
Diagnostic Agents ◽  
Perfusion Tracer

The chemical methods for the production of technetium-99m radiopharmaceuticals containing a terminal Tc<FONT FACE=Symbol>º</FONT>N triple bond have been established more than a decade ago. From that time, the chemistry of nitrido Tc-99m complexes has provided a highly efficient tool for the design and preparation of novel classes of diagnostic agents, and a number of potentially useful radiopharmaceuticals have been discovered. In particular, nitrido technetium-99m tracers have been developed for heart perfusion imaging. In this short review, the chemical and biological properties of the neutral myocardial perfusion tracer bis(N-ethoxy, N-ethyl-dithiocarbamato) nitrido Tc-99m (TcN-NOEt) will be summarized along with the preparation and preliminary biological evaluation of the first class of monocationic nitrido technetium-99m radiopharmaceuticals exhibiting improved biodistribution properties closer to those expected for an ideal perfusion imaging agent.

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