Model Reactions on the [4+2+2] Rhodium-catalyzed Cycloaddition Reaction: Toward the Total Synthesis of Asteriscanolide

Model Reactions on the [4+2+2] Rhodium-catalyzed Cycloaddition Reaction: Toward the Total Synthesis of Asteriscanolide
Author: W. Richard Counts
Publisher:
Total Pages: 309
Release: 2007
Genre:
ISBN: 9780549070566

Download Model Reactions on the [4+2+2] Rhodium-catalyzed Cycloaddition Reaction: Toward the Total Synthesis of Asteriscanolide Book in PDF, Epub and Kindle

While the total synthesis was not completed the results presented prove that the [4+2+2] reaction is a feasible step in the synthesis of complicated cyclooctanoid containing natural products. The history of the transition metal-catalyzed [m+n] and [m+n+o] cycloaddition reactions toward the synthesis of medium-sized ring systems will be discussed and compared to the results observed in this study. The case for further development of the catalytic reaction will also be presented.

Modern Rhodium-Catalyzed Organic Reactions

Modern Rhodium-Catalyzed Organic Reactions
Author: P. Andrew Evans
Publisher: John Wiley & Sons
Total Pages: 496
Release: 2006-03-06
Genre: Science
ISBN: 352760409X

Download Modern Rhodium-Catalyzed Organic Reactions Book in PDF, Epub and Kindle

Rhodium has proven to be an extremely useful metal due to its ability to catalyze an array of synthetic transformations, with quite often-unique selectivity. Hydrogenation, C-H activation, allylic substitution, and numerous other reactions are catalyzed by this metal, which presumably accounts for the dramatic increase in the number of articles that have recently emerged on the topic. P. Andrew Evans, the editor of this much-needed book, has assembled an internationally renowned team to present the first comprehensive coverage of this important area. The book features contributions from leaders in the field of rhodium-catalyzed reactions, and thereby provides a detailed account of the most current developments, including: Rhodium-Catalyzed Asymmetric Hydrogenation (Zhang) Rhodium-Catalyzed Hydroborations and Related Reactions (Brown) Rhodium-Catalyzed Asymmetric Addition of Organometallic Reagents to Electron Deficient Olefins (Hayashi) Recent Advances in Rhodium(I)-Catalyzed Asymmetric Olefin Isomerization and Hydroacylation Reactions (Fu) Stereoselective Rhodium(I)-Catalyzed Hydroformylation and Silylformylation Reactions and Their Application to Organic Synthesis (Leighton) Carbon-Carbon Bond-Forming Reactions Starting from Rh-H or Rh-Si Species (Matsuda) Rhodium(I)-Catalyzed Cycloisomerization and Cyclotrimerization Reactions (Ojima) The Rhodium(I)-Catalyzed Alder-ene Reaction (Brummond) Rhodium-Catalyzed Nucleophilic Ring Cleaving Reactions of Allylic Ethers and Amines (Fagnou) Rhodium(I)-Catalyzed Allylic Substitution Reactions and their Applications to Target Directed Synthesis (Evans) Rhodium(I)-Catalyzed [2+2+1] and [4+1] Carbocyclization Reactions (Jeong) Rhodium(I)-Catalyzed [4+2] and [4+2+2] Carbocyclizations (Robinson) Rhodium(I)-Catalyzed [5+2], [6+2], and [5+2+1] Cycloadditions: New Reactions for Organic Synthesis (Wender) Rhodium(II)-Stabilized Carbenoids Containing both Donor and Acceptor Substituents (Davies) Chiral Dirhodium(II)Carboxamidates for Asymmetric Cyclopropanation and Carbon-Hydrogen Insertion Reactions (Doyle) Cyclopentane Construction by Rhodium(II)-Mediated Intramolecular C-H Insertion (Taber) Rhodium(II)-Catalyzed Oxidative Amination (DuBois) Rearrangement Processes of Oxonium and Ammonium Ylides Formed by Rhodium(II)-Catalyzed Carbene-Transfer (West) Rhodium(II)-Catalyzed 1,3-Dipolar Cycloaddition Reactions (Austin) "Modern Rhodium-Catalyzed Organic Reactions" is an essential reference text for researchers at all levels in the general area of organic chemistry. This book provides an invaluable overview of the most significant developments in this important area of research, and will no doubt be an essential text for researchers at academic institutions and professionals at pharmaceutical/agrochemical companies.

Rhodium-catalyzed [5+1] and [5+2] Cycloadditions Using 1,4-enyne as the Five-carbon Component

Rhodium-catalyzed [5+1] and [5+2] Cycloadditions Using 1,4-enyne as the Five-carbon Component
Author: Wangze Song
Publisher:
Total Pages: 0
Release: 2016
Genre:
ISBN:

Download Rhodium-catalyzed [5+1] and [5+2] Cycloadditions Using 1,4-enyne as the Five-carbon Component Book in PDF, Epub and Kindle

Transition metal-catalyzed cycloaddition reaction is one of the most efficient ways to access ring systems and remains to be one of the most active areas in organic chemistry. The discovery of 3-acyloxy-1,4-enyne (ACE) and 3-hydroxy-1,4-enyne (HYE) as the five-carbon components has led to the development of various Rh-catalyzed [5+1] and [5+2] cycloadditions in our group. These novel methods offered efficient access to highly substituted six- and seven-membered carbocycles. I will present our progresses on the development, application and mechanistic studies of the following four [5+1] and [5+2] cycloadditions. 1) Using ACE bearing an electron-rich ester as the five-carbon component, a [5+1] cycloaddition was realized under mild conditions for the preparation of highly substituted phenols. 2) Based on our previous success on Rh-catalyzed intermolecular [5+2] cycloaddition of ACE and alkynes, a library of highly substituted tropones was successfully prepared by modifying the cycloheptatriene products derived from the [5+2] cycloaddition. 3) The scope of the Rh-catalyzed intramolecular [5+2] cycloaddition of ACE with alkenes was expanded and the Rh-catalyzed intramolecular [5+2] cycloaddition of ACE with allenes was developed for the synthesis of highly functionalized bicyclic 5-7 fused ring systems with multiple stereogenic centers. 4) Using HYE as the 5-carbon component, a [5+1] carbonylative benzannulation reaction was previously developed in our group for the synthesis of tricyclic carbazoles. The scope of this tandem reaction is now expanded to the synthesis of tetra- and even pentacyclic ring systems including furocarbazoles, thiophenocarbazole, pyrrolocarbazole, and indolocarbazole. Metal carbene intermediates are involved in most of these cycloadditions. The strategy of using propargylic esters and propargylic alcohols as the Rh(I) carbene precursor should have broad implications in transition metal catalysis and metal carbene chemistry.

Rhodium Catalysis in Organic Synthesis

Rhodium Catalysis in Organic Synthesis
Author: Ken Tanaka
Publisher: John Wiley & Sons
Total Pages: 684
Release: 2019-05-06
Genre: Science
ISBN: 3527343644

Download Rhodium Catalysis in Organic Synthesis Book in PDF, Epub and Kindle

An essential reference to the highly effective reactions applied to modern organic synthesis Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis explores the most recent progress and new developments in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes. Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource: -Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others) -Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions -Presents a volume edited by one of the international leading scientists working in the field today -Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.

Rhodium-bisphosphine Monooxide-catalyzed [4+2+2] Cycloaddition Reactions for the Synthesis of Fused Polycyclic Systems

Rhodium-bisphosphine Monooxide-catalyzed [4+2+2] Cycloaddition Reactions for the Synthesis of Fused Polycyclic Systems
Author: Gino Martin R. Canlas
Publisher:
Total Pages:
Release: 2015
Genre: Chemistry
ISBN:

Download Rhodium-bisphosphine Monooxide-catalyzed [4+2+2] Cycloaddition Reactions for the Synthesis of Fused Polycyclic Systems Book in PDF, Epub and Kindle

The synthesis of polycyclic systems, especially those that with an eight-membered ring embedded into the structure, has long been pursued due to their ubiquitousness in numerous natural product motifs. These eight-membered rings may be efficiently synthesized using metal-catalyzed higher order cycloadditions. In our studies, some cationic rhodium(I) complexes were found to catalyze a previously-discovered [4+2+2] cycloaddition between dienynes and external alkynes giving fused systems with a cycloocta-1,3,5-triene core. Upon screening of various metal complexes, ligands and solvents, a catalytically-competent, novel rhodium-BozPHOS complex, [Rh(nbd){(S,S)-Me-BozPHOS}]SbF6, was obtained using one equivalent of [Rh(nbd)Cl]2, two equivalents of the ligand (S,S)-Me-BozPHOS and two equivalents of AgSbF6. Using this complex in the [4+2+2] cycloaddition reaction provided bicyclic systems in moderate to good yields from two molecules of acyclic dienyne or a molecule of acyclic dienyne and external alkyne. Furthermore, this complex allowed the expansion of the substrate scope for this catalytic reaction involving cyclic dienynes. It was found that only dienynes with an embedded five-membered ring provided the tricyclic system in good yields. This novel rhodium complex was also applied to the [4+2+2] cycloaddition approach towards the synthesis of (±)-asteriscanolide, leading to the formation of the asteriscane skeleton. Despite this success, various selective hydrogenation and oxidation methods failed to functionalize the cyclooctatriene system due to the electronic and steric similarities of the three double bonds in the ring, thus, preventing access to the natural produc