Progress in Inorganic Chemistry (eBook)

Kenneth D. Karlin (Autor)

eBook Download: EPUB

2014 | 1. Auflage
360 Seiten
Wiley (Verlag)
978-1-118-87003-7 (ISBN)

Infos

This series provides inorganic chemists and materials scientists with a forum for critical, authoritative evaluations of advances in every area of the discipline. Volume 59 continues to report recent advances with a significant, up-to-date selection of contributions by internationally-recognized researchers.

The chapters of this volume are devoted to the following topics:
• Iron Catalysis in Synthetic Chemistry
• A New Paradigm for Photodynamic Therapy Drug Design: Multifunctional, Supramolecular DNA Photomodification Agents Featuring Ru(II)/Os(II) Light Absorbers Coupled to Pt(II) or Rh(III) Bioactive Sites
• Selective Binding of Zn2+ Complexes to Non-Canonical Thymine or Uracil in DNA or RNA.
• Progress Toward the Electrocatalytic Production of Liquid Fuels from Carbon Dioxide
• Monomeric Dinitrosyl Iron Complexes: Synthesis and Reactivity
• Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals
• Aminopyridine Iron and Manganese Complexes as Molecular Catalysts for Challenging Oxidative Transformations

Kenneth D. Karlin, PhD, is the Ira Remsen Professor of Chemistry at Johns Hopkins University. He received his PhD from Columbia University. Dr. Karlin’s bioinorganic research focuses on coordination chemistry relevant to biological and environmental processes, involving copper or heme (porphyrin-iron) complexes. Dr. Karlin’s main approach involves synthetic modeling, i.e. biomimetic chemistry. He is the winner of the prestigous F. Albert Cotton Award in Synthetic Inorganic Chemistry and the Sierra Nevada Distinguished Chemist Award, both awarded in 2009.

Inhalt

Chapter 1 Iron Catalysis in Synthetic Chemistry 1

SUJOY RANA, ATANU MODAK, SOHAM MAITY, TUHIN PATRA, AND DEBABRATA
MAITI

Chapter 2 A New Paradigm for Photodynamic Therapy Drug Design:
Multifunctional, Supramolecular DNA Photomodification Agents
Featuring Ru(II)/Os(II) Light Absorbers Coupled to Pt(II) or
Rh(III) Bioactive Sites 189

JESSICA D. KNOLL AND KAREN J. BREWER

Chapter 3 Selective Binding of Zn2ii Complexes to
Non-Canonical Thymine or Uracil in DNA or RNA 245

KEVIN E. SITERS, STEPHANIE A. SANDER, AND JANET R.
MORROW

Chapter 4 Progress Toward the Electrocatalytic Production of
Liquid Fuels from Carbon Dioxide 299

JOEL ROSENTHAL

Chapter 5 Monomeric Dinitrosyl Iron Complexes: Synthesis and
Reactivity 339

CAMLY T. TRAN, KELSEY M. SKODJE, AND EUNSUK KIM

Chapter 6 Interactions of Nitrosoalkanes/arenes, Nitrosamines,
Nitrosothiols, and Alkyl Nitrites with Metals 381

NAN XU AND GEORGE B. RICHTER-ADDO

Chapter 7 Aminopyridine Iron and Manganese Complexes as
Molecular Catalysts for Challenging Oxidative Transformations
447

ZOEL CODOLA, JULIO LLORET-FILLOL, AND MIQUEL COSTAS

Subject Index 533

Cumulative Index 561

Textauszug

Iron Catalysis in Synthetic Chemistry

Sujoy Rana, Atanu Modak, Soham Maity, Tuhin Patra, and Debabrata Maiti

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, India

CONTENTS

1. I. Introduction
2. II. Addition Reactions
   1. A. Cycloadditions
      1. 1. The [2 + 2] Cycloaddition
      2. 2. The [3 + 2] Cycloaddition
      3. 3. The [2 + 2 + 2] Cycloaddition
      4. 4. The [4 + 2] Cycloaddition
   2. B. Cyclopropanation
   3. C. Aziridination and Aziridine Ring-Opening Reactions
   4. D. Carbometalation of C—C Unsaturated Bond
   5. E. Michael Addition
   6. F. Barbier-Type Reaction
   7. G. Kharasch Reaction
3. III. The C—C Bond Formations VIA C—H Functionalization
   1. A. The C—H Arylation
      1. 1. Direct Arylation With Organometallic Reagents
      2. 2. Direct Arylation With Aryl Halides
   2. B. The C—C Bond Formation Via Cross-Dehydrogenative Coupling
      1. 1. The CDC Between Two sp3 C—H Bonds
      2. 2. The CDC Between sp3 and sp2 C—H Bonds
      3. 3. The CDC Between sp3 and sp C—H Bonds
   3. C. The C—C Bond Formation via Cross-Decarboxylative Coupling
   4. D. The C—C Bond Formation via Alkene Insertion
   5. E. Oxidative Coupling of Two C—H Bonds
4. IV. The C—H Bond Oxidation
   1. A. Hydroxylation
   2. B. Epoxidation
   3. C. cis-Dihydroxylation
5. V. Cross-Coupling Reactions
   1. A. Alkenyl Derivatives as Coupling Partners
   2. B. Aryl Derivatives as Coupling Partners
   3. C. Alkyl Derivatives as Coupling Partners
      1. 1. Low-Valent Iron Complex in Cross-Coupling Reactions
   4. D. Acyl Derivatives as Coupling Partners
   5. E. Iron-Catalyzed C—O, C—S, and C—N Cross-Coupling Reaction
   6. F. Iron-Catalyzed Mizoraki–Heck Reaction
   7. G. Iron-Catalyzed Negishi Coupling Reaction
   8. H. Suzuki–Miyaura Coupling Reaction
   9. I. Sonogashira Reaction
   10. J. Mechanism of Cross-Coupling Reactions
   11. K. Hydrocarboxylation
   12. L. Enyne Cross-Coupling Reaction
6. VI. Direct C—N Bond Formation VIA C—H Oxidation
7. VII. Iron-Catalyzed Amination
   1. A. Allylic Aminations
   2. B. Intramolecular Allylic Amination
8. VIII. Sulfoxidations and Synthesis of Sulfoximines, Sulfimides, and Sulfoximides
   1. A. Sulfoxidation
   2. B. Synthesis of Sulfoximines, Sulfimides, and Sulfoximides
      1. 1. Mechanism
9. IX. Reduction Reactions
   1. A. Hydrosilylation of Alkenes
   2. B. Hydrosilylation of Aldehydes and Ketones
   3. C. Hydrogenation of C—C Unsaturated Bonds
   4. D. Hydrogenation of Ketones
   5. E. Hydrogenation of Imines
   6. F. Reduction of Nitroarene to Anilines
   7. G. Hydrogenation of Carbon Dioxide and Bicarbonate
   8. H. Amide Reduction
   9. I. Reductive Aminations
10. X. Trifluoromethylation
11. XI. Conclusion
12. Acknowledgments
13. Abbreviations
14. References

I. Introduction

During the last few decades, transition metal catalysts, especially those on precious metals [e.g., palladium (Pd), rhodium (Rh), iridium (Ir), and ruthenium (Ru)] have proven to be efficient for a large number of applications. The success of transition metal based organometallic catalysts lies in the easy modification of their environment by ligand exchange. A very large number of different types of ligands can coordinate to transition metal ions. Once the ligands are coordinated, the reactivity of the metals may change dramatically. However, the limited availability of these metals, in order of decreasing risk (depletion): Au > Ir, Rh, Ru > Pt, Re, Pd), as well as their high price (Fig. 1) and significant toxicity, makes it desirable to search for more economical and environmental friendly alternatives. A possible solution to this problem could be the increased use of catalysts based on first-row transition metals, especially iron (Fe) (1). In contrast to synthetic precious metal catalysts, iron takes part in various biological systems as an essential key element and electron-transfer reactions.

Figure 1. Comparison of prices for different transition metals (Sigma Aldrich).

Due to its abundance, inexpensiveness, and environmentally benign nature, use of iron has increased significantly in the last two decades for synthetic transformation both in asymmetric synthesis and reaction methodology. This development encouraged us to summarize the use of iron catalysis in organic synthesis, which includes cycloadditions, C—C, C—N bond formation, redox, and other reactions. This chapter has been divided into different sections based on the reaction type.

II. Addition Reactions

A. Cycloadditions

1. The [2 + 2] Cycloaddition

In 2001, Itoh and co-workers (2) demonstrated the [2 + 2] cyclodimerization of trans-anethol catalyzed by alumina supported iron(III) perchlorate. A C2 symmetric cyclobutane derivative was obtained in excellent yield (92%) at room temperature (rt), though longer reaction time was required. They applied the same catalytic system for the cycloaddition of styrenes and quinones. However, 2,3-dihydrobenzofuran derivatives were obtained in excellent yields in place of the desired [2 + 2] cycloadduct (Scheme 1) (3). Earlier, in 1982, Rosenblum and Scheck (4) showed that the CpFe(CO)2 cation, where Cp = cyclopentadienyl, could afford the unsaturated bicycle through the reaction of alkenes and methyl tetrolate, though the yields obtained were inferior.

Scheme 1. Early examples of iron-catalyzed [2 + 2] cycloaddition.

Significant improvement in iron-catalyzed [2 + 2] cycloaddition was achieved in 2006 by Chirik and co-workers (5). They reported an intramolecular [2 + 2] cycloaddition of the dienes resulting in the formation of [0.2.3] heptane derivatives catalyzed by a bis(imino)-pyridine iron(II) bis(dinitrogen) complex and only cis product was obtained. Further, labeling experiments confirmed the reaction to be stereospecific. A number of dienes containing different amine and ester functional groups reacted efficiently, but the presence of secondary amine and an SiMe2 group inhibited the reaction. This reaction can also be performed in the dark, clearly indicating the process to be thermally driven, rather than a photochemical one. A mechanism of this catalytic process was proposed where iron is assumed to maintain its ferrous oxidation state throughout the reaction with the help of redox active iPrPDI ligand (Scheme 2).

Scheme 2. Plausible mechanism involving the iron(II) oxidation state [PDI = (N,N′,E,N,N′,E)-N,N′-(1,1′)-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidine))bis(2,6-diisopropylaniline)].

A combination of ethylene and butadiene resembles a thermally allowed [4 + 2] cycloaddition reaction, namely, the Diels–Alder reaction. Using their redox-active bis(imino)-pyridine supported iron catalysts, Chirik and co-workers (6) reported the more challenging [2 + 2] cycloaddition from the same set of starting materials that furnished vinylcyclobutane in an excellent 95% yield. The protocol turned out to be substrate specific, as with insertion of a methyl group in the 2- position of diene, no cycloadduct was observed; rather it resulted in a 1,4-addition product. To shed light on their plausible mechanism, several labeling experiments were carried out with different substrates. They were successful in intercepting one iron metallocyclic intermediate, which resulted from ethylene insertion into the coordinated diene. The same species was also prepared by reacting vinylcyclobutane, the product of the [2 + 2] cycloaddition, with the iron catalyst. Thus the reaction proved to be reversible with iron metallocycle as an intermediate, and the backward reaction demonstrated a rare example of sp3–sp3 C—C bond activation with an iron catalyst under mild conditions. Isolation of the metallocycle intermediate and labeling experiments led to a proposed mechanism for [2 + 2] cycloaddition and 1,4-addition. The reaction initiated by displacement of dinitrogen ligands by diene an η4 complex, and ethylene insertion, which furnished the isolable metallocycle intermediate. In the next step, butadiene-induced reductive-elimination resulted in vinylcyclobutane along with regeneration of an iron butadiene intermediate. However, with isoprene, β-hydrogen elimination followed by C—H reductive elimination resulted in the 1,4-addition product (Scheme 3).

Scheme 3. Proposed mechanism for [2 + 2] cycloaddition of ethylene and butadiene.

2. The [3 + 2]...

Produkt-Details

• Erscheint lt. Verlag: 22.7.2014
• Reihe/Serie: Progress in Inorganic Chemistry
• Reihe/Serie: Progress in Inorganic Chemistry
• Reihe/Serie: Progress in Inorganic Chemistry
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Biologie ► Biochemie
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Technik ► Maschinenbau
• Schlagworte: Advances • Anorganische Chemie • area • authoritative • Bioanorganische Chemie • bioinorganic chemistry • Chemie • Chemistry • Chemists • Continues • Critical • Discipline • Edge • Evaluations • every • Forum • inorganic • Inorganic Chemistry • internationallyrecognized • Materials Science • Materialwissenschaften • Progress • Recent Advances • Reporting • Scientific • series • significant • Tradition • Volume
• ISBN-10: 1-118-87003-4 / 1118870034
• ISBN-13: 978-1-118-87003-7 / 9781118870037