Recent Developments in Heck-Type Reaction of Unactivated Alkenes and Alkyl Electrophiles

Synthesis ◽  
2020 ◽  
Author(s):  
Lili Shi ◽  
Junkai Fu ◽  
Shuangqiu Gao ◽  
Le Chang ◽  
Binglin Wang
Keyword(s):  
Heck Reaction ◽  
Alkyl Radicals ◽  
Type Reaction ◽  
The Past ◽  
Alkyl Electrophiles ◽  
Recent Developments ◽  
Palladium Catalyzed ◽  
Initial Work ◽  
Activated Olefins ◽  
Pseudo Halides

AbstractThe Mizoroki–Heck reaction is considered as one of the most ingenious and widely used methods for constructing C–C bonds. This reaction mainly focuses on activated olefins (styrenes, acrylates, or vinyl ethers) and aryl/vinyl (pseudo) halides. In comparison, the studies on unactivated alkenes and alkyl electrophiles are far less due to the low reactivity, poor selectivity, as well as competitive β-H elimination. In the past years, a growing interest has thus been devoted and significant breakthroughs have been achieved in the employment of unactivated alkenes and alkyl electrophiles as the reaction components, and this type of coupling is called as Heck-type or Heck-like reaction, which distinguishes from the traditional Heck reaction. Herein, we give a brief summary on Heck-type reaction between unactivated alkenes and alkyl electrophlies, covering its initial work, recent advancements, and mechanistic discussions.1 Introduction2 Intramolecular Heck-Type Reaction of Unactivated Alkenes and Alkyl Electrophiles2.1 Cobalt-Catalyzed Intramolecular Heck-Type Reaction2.2 Palladium-Catalyzed Intramolecular Heck-Type Reaction2.3 Nickel-Catalyzed Intramolecular Heck-Type Reaction2.4 Photocatalysis and Multimetallic Protocol for Intramolecular Heck-Type Reaction3 Intermolecular Heck-Type Reaction of Unactivated Alkenes and Alkyl Electrophiles3.1 Electrophilic Trifluoromethylating Reagent as Reaction Partners3.2 Alkyl Electrophiles as Reaction Partners4 Oxidative Heck-Type Reaction of Unactivated Alkenes and Alkyl Radicals5 Conclusions and Outlook

scholarly journals Recent Advances in Palladium-Catalyzed Isocyanide Insertions

Molecules ◽  
2020 ◽  
Vol 25 (21) ◽  
pp. 4906
Author(s):  
Jurriën W. Collet ◽  
Thomas R. Roose ◽  
Bram Weijers ◽  
Bert U. W. Maes ◽  
Eelco Ruijter ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Building Blocks ◽  
Insertion Reactions ◽  
Chemical Reagents ◽  
The Past ◽  
Recent Advances ◽  
Recent Developments ◽  
Palladium Catalyzed ◽  
Made In ◽  
Rapid Incorporation

Isocyanides have long been known as versatile chemical reagents in organic synthesis. Their ambivalent nature also allows them to function as a CO-substitute in palladium-catalyzed cross couplings. Over the past decades, isocyanides have emerged as practical and versatile C1 building blocks, whose inherent N-substitution allows for the rapid incorporation of nitrogeneous fragments in a wide variety of products. Recent developments in palladium catalyzed isocyanide insertion reactions have significantly expanded the scope and applicability of these imidoylative cross-couplings. This review highlights the advances made in this field over the past eight years.

A palladium/Et3N·HI-catalyzed highly selective 7-endo alkyl-Heck-type reaction of epoxides and a DFT study on the mechanism

2021 ◽  
Author(s):  
Xu Dong ◽  
Li-Ping Xu ◽  
Yi Yang ◽  
Yunxia Liu ◽  
Xin Li ◽  
...  
Keyword(s):  
Heck Reaction ◽  
Ring Opening ◽  
Dft Study ◽  
Type Reaction ◽  
Highly Efficient ◽  
Palladium Catalyzed ◽  
Ring Opening Of Epoxides

A highly efficient 7-endo alkyl-Heck reaction was achieved via palladium catalyzed ring-opening of epoxides, providing a variety of 6-aryl-2,3,4,7-tetrahydro-1H-azepin-3-ols and 6-aryl-2,3,4,5-tetrahydrooxepin-3-ols.

scholarly journals Recent Developments in Palladium-Catalyzed Asymmetric Intermolecular Heck Reaction

2014 ◽  
Vol 72 (7) ◽  
pp. 765 ◽  
Author(s):  
Hao Li ◽  
Changhua Ding ◽  
Bin Xu ◽  
Xuelong Hou
Keyword(s):  
Heck Reaction ◽  
Recent Developments ◽  
Palladium Catalyzed

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Copper Catalyzed sp3 C-H α-Acetylation

2019 ◽  
Author(s):  
Otome Okoromoba ◽  
Eun Sil Jang ◽  
Claire McMullin ◽  
Thomas Cundari ◽  
Timothy H. Warren
Keyword(s):  
Natural Products ◽  
Dft Studies ◽  
Alkyl Radicals ◽  
Important Chemical ◽  
Alkyl Electrophiles ◽  
Synthetic Intermediates ◽  
Alkylation Reactions

<p>α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp<sup>3</sup> C-H α-acetylation of sp<sup>3</sup> C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH<sub>2</sub>R at RT with <sup>t</sup>BuOO<sup>t</sup>Bu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [Cu<sup>II</sup>](CH<sub>2</sub>C(O)Ar) that capture alkyl radicals R• to give R-CH<sub>2</sub>C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH<sub>2</sub>CH<sub>2</sub>C(O)Ar.</p>

Wilfred Ethier. Modern International Economics. New York: W. W. Norton and Company. 1983. xviii + 588 pp.

1988 ◽  
Vol 27 (1) ◽  
pp. 81-83
Author(s):  
Nadeem A. Burney
Keyword(s):  
International Economic ◽  
New York ◽  
Economic Theory ◽  
International Economics ◽  
International Monetary System ◽  
International Markets ◽  
The Past ◽  
Monetary System ◽  
Recent Developments

Its been long recognized that various economies of the world are interlinked through international trade. The experience of the past several years, however, has demonstrated that this economic interdependence is far greater than was previously realized. In this context, the importance of international economic theory as an area distinct from general economics hardly needs any mentioning. What gives international economic theory this distinction is international markets for some goods and effects of national sovereignty on the character of economic activity. Wilfred Ethier's book, which incorporates recent developments in the field, is an excellent addition to textbooks on international economics for one- or twosemester undergraduate courses. The book mostly covers standard topics. A distinguishing feature of this book is its detailed analysis of the flexible exchange rates and a discussion of the various approaches used for their determination. Within each chapter, the author has extensively used facts, figures and major events to clarify the concepts in the light of the theoretical framework. The book also discusses, in a fair amount of detail, the existing international monetary system and the role of various international organizations.

Developments in sugarcane processing over the past 15 years

2019 ◽  
pp. 451-458
Author(s):  
Peter W. Rein
Keyword(s):  
Environmental Conditions ◽  
Energy Value ◽  
The Past ◽  
Recent Developments ◽  
Technology Of Production ◽  
Sugarcane Processing

Developments in the technology of production of sugar from sugarcane tend to be incremental improvements in an effort to reduce costs and boost revenue. Nonetheless the developments are significant and contribute to sustainable sugarcane enterprises. Some technologies have adapted to changing environmental conditions, and more attention is being given to boosting revenue through associated activities, particularly in enhancing the potential for sugarcane operations to exploit the energy value of sugarcane. This paper outlines recent developments of interest in processing sugarcane.

Performing States-Of-In-Between: Dogs, Parrots, and Other Humans in Recent Austrian Performances

2017 ◽  
Vol 40 (3) ◽  
pp. 295-310
Author(s):  
Sabine Wilke
Keyword(s):  
Fine Arts ◽  
Specific Form ◽  
Cultural Critique ◽  
Contemporary Society ◽  
Dramatic Effect ◽  
The Past ◽  
Violent Content ◽  
The World ◽  
The Sixties ◽  
Recent Developments

Every late spring since 1951, the Wiener Festwochen bring performers from around the world to Vienna for an opportunity to share recent developments in performance styles and present them to a Viennese public that seems to be increasingly open to experimentation. These festival weeks solidify a specific form of Viennese self-understanding and self-representation as a culture that is rooted in performance. This essay seeks to link two recent Austrian performances—one of them was part of the Wiener Festwochen in 2016, the other was staged in downtown Linz during the past few years—to this Austrian and specifically Viennese culture of performance by reading them as contemporary articulations of a tradition of radical performance art that can be traced back to the Viennese Actionism of the sixties and later feminist articulations in the seventies and eighties. They play on the dramatic effect of these actions, specifically their joy in cruelty, chaos, and orgiastic intoxication, by staging regressions and thus making visible what has been dammed up and repressed in contemporary society.1 Just as their historical models, these two performances merge the performing and the fine arts and they highlight provocative, controversial, and, at times, violent content. But they do it in an interspecies context that adds an entire layer of complexity to the project of societal and cultural critique.

The Medicinal Chemistry of Therapeutic Peptides: Recent Developments in Synthesis and Design Optimizations

2019 ◽  
Vol 26 (13) ◽  
pp. 2330-2355 ◽  
Author(s):  
Anutthaman Parthasarathy ◽  
Sasikala K. Anandamma ◽  
Karunakaran A. Kalesh
Keyword(s):  
High Throughput ◽  
High Throughput Screening ◽  
Therapeutic Potential ◽  
The Past ◽  
Recombinant Production ◽  
Tremendous Progress ◽  
Recent Developments ◽  
Therapeutic Peptides ◽  
Development Processes ◽  
Delivery Strategies

Peptide therapeutics has made tremendous progress in the past decade. Many of the inherent weaknesses of peptides which hampered their development as therapeutics are now more or less effectively tackled with recent scientific and technological advancements in integrated drug discovery settings. These include recent developments in synthetic organic chemistry, high-throughput recombinant production strategies, highresolution analytical methods, high-throughput screening options, ingenious drug delivery strategies and novel formulation preparations. Here, we will briefly describe the key methodologies and strategies used in the therapeutic peptide development processes with selected examples of the most recent developments in the field. The aim of this review is to highlight the viable options a medicinal chemist may consider in order to improve a specific pharmacological property of interest in a peptide lead entity and thereby rationally assess the therapeutic potential this class of molecules possesses while they are traditionally (and incorrectly) considered ‘undruggable’.

scholarly journals Bio-Based Alternatives to Phenol and Formaldehyde for the Production of Resins

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2237 ◽  
Author(s):  
P. R. Sarika ◽  
Paul Nancarrow ◽  
Abdulrahman Khansaheb ◽  
Taleb Ibrahim
Keyword(s):  
Raw Materials ◽  
Phenol Formaldehyde ◽  
Raw Material ◽  
Wood Industry ◽  
Suitable Material ◽  
The Past ◽  
Wide Range ◽  
Recent Developments ◽  
Sustainable Materials ◽  
Materials Used

Phenol–formaldehyde (PF) resin continues to dominate the resin industry more than 100 years after its first synthesis. Its versatile properties such as thermal stability, chemical resistance, fire resistance, and dimensional stability make it a suitable material for a wide range of applications. PF resins have been used in the wood industry as adhesives, in paints and coatings, and in the aerospace, construction, and building industries as composites and foams. Currently, petroleum is the key source of raw materials used in manufacturing PF resin. However, increasing environmental pollution and fossil fuel depletion have driven industries to seek sustainable alternatives to petroleum based raw materials. Over the past decade, researchers have replaced phenol and formaldehyde with sustainable materials such as lignin, tannin, cardanol, hydroxymethylfurfural, and glyoxal to produce bio-based PF resin. Several synthesis modifications are currently under investigation towards improving the properties of bio-based phenolic resin. This review discusses recent developments in the synthesis of PF resins, particularly those created from sustainable raw material substitutes, and modifications applied to the synthetic route in order to improve the mechanical properties.

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