Recent Developments in the Metal-Catalyzed Reactions of Metallocarbenoids from Propargylic Esters

ChemInform ◽  
2007 ◽  
Vol 38 (20) ◽  
Author(s):  
Jose Marco-Contelles ◽  
Elena Soriano
Keyword(s):  
Recent Developments ◽  
Propargylic Esters ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Diels–Alder Reactions of 1,2-Dihydropyridines: An Efficient Tool for the Synthesis of Isoquinuclidines

Synthesis ◽  
2018 ◽  
Vol 50 (09) ◽  
pp. 1773-1782 ◽  
Author(s):  
Eduarda Silva ◽  
Artur Silva ◽  
Djenisa Rocha
Keyword(s):  
Alder Reaction ◽  
Diels Alder ◽  
Efficient Tool ◽  
Organometallic Catalysts ◽  
Diels Alder Reaction ◽  
Straightforward Method ◽  
Recent Developments ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Valuable Compounds

The Diels–Alder reaction of 1,2-dihydropyridines with different dienophiles is a well-established and straightforward method for the synthesis of isoquinuclidines. Nevertheless, the enantioselective preparation of isoquinuclidines using organocatalysts or organometallic catalysts is rather unexplored. This succinct review offers readers an overall perspective of the most important recent developments and concepts related to this topic.1 Introduction2 Asymmetric Diels–Alder Reaction of 1,2-Dihydropyridines2.1 Transition-Metal-Catalyzed Reactions2.2 Organocatalyzed Reactions3 Diels–Alder Reaction of 1,2-Dihydropyridines in the Synthesis of Biologically Valuable Compounds4 Conclusion

Organometallic catalysts in synthetic organic chemistry: From reactions in aqueous media to gold catalysis

2008 ◽  
Vol 80 (5) ◽  
pp. 831-844 ◽  
Author(s):  
Jean-Pierre Genêt ◽  
Sylvain Darses ◽  
Véronique Michelet
Keyword(s):  
Aqueous Media ◽  
Gold Catalysis ◽  
Catalytic Reactions ◽  
Organometallic Catalysts ◽  
Water As Solvent ◽  
Recent Developments ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Simplified Procedures ◽  
Significant Attention

Water has attracted significant attention as an alternative solvent for transition-metal-catalyzed reactions. The use of water as solvent allows simplified procedures for separation of the catalyst from the products and recycling of the catalyst. Water is an inexpensive reagent for the formation of oxygen-containing products such as alcohols. The use of water as a medium for promoting organometallic and organic reactions is also of great potential. This chapter will focus on old and recent developments in the design and applications of some catalytic reactions using aqueous-phase Pd, Rh, Pt, and Au complexes.

Preface

2006 ◽  
Vol 78 (2) ◽  
pp. vi
Author(s):  
Alexandre Alexakis
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Nobel Prize ◽  
Materials Chemistry ◽  
Organometallic Reagents ◽  
High Profile ◽  
Recent Developments ◽  
Oral Communications ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

The 13th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-13<http://omcos13.unige.ch/>) was held in Geneva, Switzerland, from 17-21 July 2005.The aim of this series of symposia is to bring together chemists from academia and industry to define and discuss the most recent developments in the areas of catalysis, new organometallic reagents and reactions, and new materials chemistry. In 2001, Sharpless, Noyori, and Knowles received the Nobel Prize for their work in this area of chemistry; and the high profile has been maintained by the award of the 2005 Nobel Prize in Chemistry to Chauvin, Grubbs, and Schrock for the development of the metathesis method in organic synthesis.OMCOS-13 had a record number of nearly 1200 participants from 41 countries, and there was an encouragingly high proportion of young scientists in attendance. Very strong Asian participation at this conference reflected the outstanding level of research and leadership in this field from countries such as Japan, China, South Korea, and Taiwan.Prof. Shengming Ma, from the Shanghai Institute of Organic Chemistry of the Chinese Academy of Science and the Department of Chemistry, Zhejiang University, China received the OMCOS-13 Award (sponsored by the Yen Chuang Foundation and Springer Verlag). The prize was awarded for his creative research contributions in the field of transition-metal-catalyzed reactions of allenes.Apart from the OMCOS-13 Award lecture, there were 23 plenary lectures and 20 oral communications that dealt with aspects of reactivity and chemoselectivity of main group and transition-metal organometallics. Stereoselectivity issues also figured prominently with a particular emphasis on asymmetric synthesis and catalysis. Mechanistic insights, new reagents for synthesis, new catalyst and ligand design, and ligand effects were other important topics.The quality of the 620 posters that were on display during the entire conference was also outstanding. This extraordinary poster session was highlighted with the Monday evening "poster party" and culminated in the awarding of 37 poster prizes.OMCOS-13 was held as a single session conference in an impressive lecture theater and a large exhibition area in the center of Geneva at a superb lakefront location. It was a fitting venue for the firstclass science that was presented.Thirty-seven lecturers of OMCOS-13 present their chemistry in this issue of Pure and Applied Chemistry and provide a fine recollection of last summer's conference. The 14th edition of OMCOS will be held in Nara, Japan (2-6 August 2007) under the chairmanship of Prof. Koichiro Oshima.Alexandre AlexakisOMCOS-13 Co-chairE. Peter KündigOMCOS-13 Co-chair

Hypervalent Iodine Reagents for Oxidative Rearrangements

2020 ◽  
Vol 17 ◽  
Author(s):  
Samata E. Shetgaonkar ◽  
Manjula Krishnan ◽  
Fateh V. Singh
Keyword(s):  
Hypervalent Iodine ◽  
Organic Transformations ◽  
Cyclization Reactions ◽  
Bond Functionalization ◽  
Oxidative Functionalization ◽  
Oxidative Rearrangement ◽  
Recent Developments ◽  
Electrophilic Reagents ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

: The chemistry of hypervalent iodine reagents have emerged as an astonishing field in synthetic organic chemistry owing to its easy availability and environment benign features. Hypervalent iodine reagents are mostly employed as an alternative in various metal catalyzed reactions since they show similar reactivity to the transition metals, are less toxic and less expensive. These reagents are often used as oxidant as well as electrophilic reagents in number of organic transformations such as oxidative functionalization, alpha C-H bond functionalization of carbonyl compounds, rearrangements and cyclization reactions. Furthermore, the application of iodine(III) and iodine(V) reagents in various oxidative rearrangement processes generating diverse array of molecules have been well explored. In this mini review, we have covered the recent developments in the area of oxidative rearrangements using hypervalent iodine reagents.

Monodentate Trialkylphosphines: Privileged Ligands in Metal-catalyzed Crosscoupling Reactions

2020 ◽  
Vol 24 (3) ◽  
pp. 231-264 ◽  
Author(s):  
Kevin H. Shaughnessy
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Bromides ◽  
Wide Range ◽  
Sterically Demanding ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phosphines are widely used ligands in transition metal-catalyzed reactions. Arylphosphines, such as triphenylphosphine, were among the first phosphines to show broad utility in catalysis. Beginning in the late 1990s, sterically demanding and electronrich trialkylphosphines began to receive attention as supporting ligands. These ligands were found to be particularly effective at promoting oxidative addition in cross-coupling of aryl halides. With electron-rich, sterically demanding ligands, such as tri-tertbutylphosphine, coupling of aryl bromides could be achieved at room temperature. More importantly, the less reactive, but more broadly available, aryl chlorides became accessible substrates. Tri-tert-butylphosphine has become a privileged ligand that has found application in a wide range of late transition-metal catalyzed coupling reactions. This success has led to the use of numerous monodentate trialkylphosphines in cross-coupling reactions. This review will discuss the general properties and features of monodentate trialkylphosphines and their application in cross-coupling reactions of C–X and C–H bonds.

Chemistry of Unsymmetrical C1-Substituted Oxabenzonorbornadienes

2021 ◽  
Vol 17 ◽  
Author(s):  
Austin Pounder ◽  
Angel Ho ◽  
Matthew Macleod ◽  
William Tam
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Substituent Effects ◽  
Face Selectivity ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Synthetic Intermediate

: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate which can be readily activated by transition metal complexes with great face selectivity due to its dual-faced nature and intrinsic angle strain on the alkene. To date, the understanding of transition-metal catalyzed reactions of OBD itself has burgeoned; however, this has not been the case for unsymmetrical OBDs. Throughout the development of these reactions, the nature of C1-substituent has proven to have a profound effect on both the reactivity and selectivity of the outcome of the reaction. Upon substitution, different modes of reactivity arise, contributing to the possibility of multiple stereo-, regio-, and in extreme cases, constitutional isomers which can provide unique means of constructing a variety of synthetically useful cyclic frameworks. To maximize selectivity, an understanding of bridgehead substituent effects is crucial. To that end, this review outlines hitherto reported examples of bridgehead substituent effects on the chemistry of unsymmetrical C1-substituted OBDs.

Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account

1994 ◽  
Vol 59 (1) ◽  
pp. 1-74 ◽  
Author(s):  
Pavel Kočovský
Keyword(s):  
Transition Metals ◽  
Cyclopropane Ring ◽  
Allylic Substitutions ◽  
Recent Developments ◽  
Cardioactive Drug ◽  
Novel Method ◽  
Metal Catalyzed ◽  
Electrophilic Additions ◽  
Near Future ◽  
First Time

This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.

scholarly journals Transition metal-catalyzed reactions of N-sulfinyl imines

2021 ◽  
pp. 153104
Author(s):  
Francisco Foubelo ◽  
Carmen Nájera ◽  
José M. Sansano ◽  
Miguel Yus
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

scholarly journals Chiral Aziridine Sulfide N(sp3),S-Ligands for Metal-Catalyzed Asymmetric Reactions

Symmetry ◽  
2021 ◽  
Vol 13 (3) ◽  
pp. 502
Author(s):  
Agata J. Pacuła-Miszewska ◽  
Anna Laskowska ◽  
Anna Kmieciak ◽  
Mariola Zielińska-Błajet ◽  
Marek P. Krzemiński ◽  
...  
Keyword(s):  
Metal Binding ◽  
Electronic Effect ◽  
Asymmetric Reactions ◽  
Addition Reactions ◽  
Phenyl Sulfide ◽  
Enantiomeric Ratio ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Sulfide Group

A series of new bidentate N,S-ligands—aziridines containing a para-substituted phenyl sulfide group—was synthesized and evaluated in the Pd-catalyzed Tsuji–Trost reaction and addition of diethylzinc and phenylethynylzinc to benzaldehyde. A high enantiomeric ratio for the addition reactions (up to 94.2:5.8) was obtained using the aziridine ligand bearing a p-nitro phenyl sulfide group. Collected results reveal a specific electronic effect that, by the presence of particular electron-donating or electron-withdrawing groups in the PhS- moiety, influences the σ-donor–metal binding and the enantioselectivity of the catalyzed reactions.

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