Regio- And Stereo-Controlled Oxidations and Reductions, Volume 5

ISBN-13: 9780470090220 / Angielski / Twarda / 2007 / 336 str.

John Whittall

Opis

Volume 5 in the Catalysts for Fine Chemical Synthesis series describes new procedures for the regio- and stereo-controlled transformations of compounds involving oxidation or reduction reactions. It describes a wide range of catalysts, including organometallic systems, biocatalysts and biomimetics. This volume also includes descriptions of a variety of conversions, including: Baeyer-Villiger oxidations; Epoxidation reactions; Hydroxylation reactions; Oxidation of alcohols to aldehydes, ketones and carboxylic acids; Reduction of ketones; and Reduction of alkenes including α, β-unsaturated carbonyl compounds. The book will be an important text for practising synthetic organic chemists in industry and academia.

• Protocols are written in a standard format by the authors who have discovered them
• Hints, tips and safety advice (where appropriate) is given to ensure that the procedures are reproducible
• Indications are given as to the range of starting materials used and, where appropriate, comparisons to alternative methodology
• Includes relevant references to the primary literature.

Spis treści

CHAPTER 1: Industrial Catalysts for Regio– or Stereo– selective Oxidations and Reductions. A Review of Key Technologies and Targets.
J. Whittall

CHAPTER 2: Asymmetric Hydrogenation of Alkenes, Enones, Ene–esters and Ene–Acids

2.1: (S)–2,2′– Bis{[di(4–methoxyphenyl)phosphinyl]oxy}–5,5′,6,6′,7,7′,8,8′–octahydro–1,1′–binaphthyl as a Ligand for Rhodium–Catalysed Asymmetric Hydrogenation
I. Gergely, C. Hegeds and J. Bakos.

2.2: Synthesis and Application of Phosphinite Oxazoline Iridium Complexes for the Asymmetric Hydrogenation of Alkenes
F. Menges and A. Pfaltz.

2.3: Synthesis and Application of Heterocyclic Phosphine Oxazoline (HetPHOX) Iridium Complexes for the Asymmetric Hydrogenation of Alkenes
F. Menges and P.G. Cozzi.

2.4: (R)–2,2′,6,6′– Tetramethoxy–bis[di(3,5–dimethylphenyl)phosphino]–3,3′–bipyridine [(R)–Xyl–P–Phos] as a Ligand for Rhodium–Catalysed Asymmetric Hydrogenation of a–Dehydroamino Acids
J. Wu and A.S.C. Chan.

2.5: (R,R)–2,3–Bis(tert–butylmethylphosphine)quinoxaline (Quinox P∗) as a Ligand for Rhodium–Catalysed Asymmetric Hydrogenation of Prochiral Amino Acid and Amine Derivatives
T. Imamoto and A. Koide.

2.6: Rhodium–Catalysed Asymmetric Hydrogenation of Indoles
R. Kuwano and M. Sawamura.

CHAPTER 3: Asymmetric Reduction of Ketones

3.1: (R,R)–Bis(diphenylphosphino)–1,3–diphenylpropane as a Versatile Ligand for Enantioselective Hydrogenations
N. Dubrovina and A. Borner.

3.2: Synthesis of Both Enantiomers of 1–Phenylethanol by Reduction of Acetophenone with Geotrichum candidum IFO 5767
K. Nakamura, M. Fujii and Y. Ida.

3.3: Titanocene–Catalysed Reduction of Ketones in the Presence of Water. A Convenient Procedure for the Synthesis of Alcohols by Free–Radical Chemistry
A. Rosales, J.M. Cuerva and J.E. Oltra.
3.4: Xyl–TetraPHEMP: A Highly Efficient Biaryl Ligand in the [Diphosphine RuCl2–diamine]–Catalysed Hydrogenation of Simple Aromatic Ketones
P.H. Moran, J.P. Henschke, A. Zanotti–Gerosa and I C. Lennon.

3.5: N–Arenesulfonyl– and N–Alkylsulfamoyl–1,2–diphenylethylenediamine Ligands for Ruthenium–Catalysed Asymmetric Transfer Hydrogenation of Activated Ketones
M.S. Stephan and B. Mohar.

3.6: The Synthesis and Application of BrXUPHOS: A Novel Monodentate Phosphorus Ligand for the Asymmetric Hydrogenation of Ketones
M. Wills, Y. Xu, G. Docherty and G. Woodward.

3.7: In Situ Formation of Ligand and Catalyst: Application in Ruthenium–Catalysed Enantioselective Reduction of Ketones
J. Wettergren and H. Adolfsson.

3.8: SYNPHOS and DIFLUORPHOS as Ligands for Ruthenium–Catalysed Hydrogenation of Alkenes and Ketones
S. Jeulin, V. Ratovelomanana–Vidal and J–P. Genet.

3.9: An Arene Ruthenium Complex with Polymerizable Side–chains for the Synthesis of Immobilised Catalysts
E. Burri, S.B. Wendicke, K. Severin.

3.10: Selective Reduction of Carbonyl Group in beta, gamma– Unsaturated alpha– Ketoesters by Transfer Hydrogenation with Ru–(para–cymene) (TsDPEN)
M. Guo, D. Li, Y. Sun and Z. Zhang.

3.11: Preparation of Polymer–Supported Ru–TsDPEN Catalysts and their Use for the Enantioselective Synthesis of (S)–Fluoxetine
L. Chai, Y. Li and Q. Wang.

3.12: Polymer–Supported Chiral Sulfonamide–Catalysed Reduction of B–Keto Nitrile: a Practical Synthesis of (R)–Fluoxetine
G.Wang and G. Zhao.

CHAPTER 4: Imine Reduction and Reductive Amination

4.1: Metal–Free Reduction of Imines: Enantioselective Bronsted Acid–Catalysed Transfer Hydrogenation using Chiral BINOL–Phosphates as Catalysts
M. Rueping, E. Sugiono, C. Azap and T. Theissmann.

4.2: Metal–Free Bronsted Acid–Catalysed Transfer Hydrogenation: Enantioselective Synthesis of Tetrahydroquinolines
M. Rueping , T. Theissmann and A. P. Antonchick.

4.3: A Highly Stereoselective Synthesis of 3a–Amino–23,24–bisnor–5a–cholane via Reductive Amination
S. N. Khan, N.J. Cho and H–S. Kim.

CHAPTER 5: Oxidation of Primary and Secondary Alcohols

5.1: Copper (II)–Catalysed Oxidation of Primary Alcohols to Aldehydes with Atmospheric Oxygen
S. Jammi and T. Punniyamurthy.

5.2: Solvent–free Dehydrogenation of Secondary Alcohols in the Absence of Hydrogen Abstractors using Robinson′s Catalyst
G.B.W.L. Ligthart, R.H. Meijer, J. v. Buijtenen, J. Meuldijk, J.A.J.M. Vekemans and L. A. Hulshof.

5.3: 2–Iodoxybenzoic Acid (IBX)/ n–Bu4NBr/ CH2Cl2–H2O: a Mild System for the Selective Oxidation of Secondary Alcohols
K. Kittigowittana, M. Pohmakotr, V. Reutrakul and C. Kuhakarn.

CHAPTER 6: Hydroxylation, Epoxidation and Related Reactions

6.1: Proline–Catalysed a–Aminoxylation of Aldehydes and Ketones
Y. Hayashi and M. Shoji.

6.2: Ru/ Silica∗ Cat∗ TEMPO(c)–Mediated Oxidation of Alkenes to a–Hydroxyacids
R. Ciriminna and M. Pagliaro.

6.3: Catalytic Enantioselective Epoxidation of trans–Disubstituted and Trisubstituted Alkenes with Arabinose–Derived Ulose
T.K. M. Shing, G.Y.C. Leung and T. Luk.

6.4: VO(acac)2/ TBHP–Catalysed Epoxidation of 2–(2–Alkenyl)phenols. Highly Regio– and Diastereo–selective Oxidative Cyclisation to 2,3–Dihydrobenzofuranols and 3–Chromanols
A. Lattanzi and A. Scettri.

6.5: An Oxalolidinone Ketone Catalyst for the Asymmetric Epoxidation of cis–Olefins
D. Goeddel and Y. Shi.

6.6: a–Fluorotropinone Immobilised on Silica: a New Stereoselective Heterogeneous Catalyst for Epoxidation of Alkenes with Oxone
G. Sartori, A. Armstrong, R. Maggi, A. Mazzacani, R. Sartorio, F. Bigi and B. Dominguez–Fernandez.

6.7: Asymmetric Epoxidation Catalysed by Novel Azacrown Ether–Type Chiral Quaternary Ammonium Salts under Phase–Transfer Catalytic Conditions
K. Hori, K. Tani, and Y. Tohda.

6.8: Enantioselective Epoxidation of Olefins using Phase–Transfer Conditions and [6–N–((S)–1,2,2–Trimethylpropyl)–5H–dibenz[c,e]azepinium] [rac–TRISPHAT] Salt as Catalyst
J. Vachon, C. Perollier, A. Martinez and J. Lacour.

6.9: Catalytic Asymmetric Epoxidation of a,Unsaturated Esters Promoted by a Yttrium–Biphenyldiol Complex
M. Shibasaki, H. Kakei and S. Matsunaga..

6.10: Catalytic Enantioselective Epoxidation of a, –Enones with a BINOL–Zinc Complex
A. Minatti and K.H. Dotz

6.11: Asymmetric Epoxidation of Phenyl 2–(3′–Pyridylvinyl) Sulfone using Polyleucine/ Hydrogen Peroxide Gel
M. Pitts and J. Whittall.

CHAPTER 7: Oxidation of Ketones to Lactones or Enones

7.1: Synthesis of 2–(Phosphinophenyl)pyridine Ligand and its Application to Palladium–Catalysed Asymmetric Baeyer– Villiger Oxidation of Prochiral Cyclobutanones
K. Ito and T. Katsuki.

7.2: (D)–Codeinone from (D)–Dihydrocodeinone via the Use of Modified o–Iodoxybenzoic Acid (IBX)
P. Mather and J. Whittall.

CHAPTER 8: Oxidative C–C Coupling

8.1: Enantioselective Oxidative Coupling of 2–Naphthols Catalysed by a Novel Chiral Vanadium Complex
N–S. Xie, Q–Z. Liu, Z–B. Luo, L–Z. Gong, A–Q. Mi and Y–Z. Jiang.

8.2: Catalytic Oxidative Cross–Coupling Reaction of 2–Naphthol Derivatives
S. Habaue and T. Temma.

8.3: Oxidative Coupling of Benzene with a,–Unsaturated Aldehydes by Pd(OAc)2/ HPMoV/ O2 System
T. Yamada, S. Sakaguchi and Y. Ishii.

CHAPTER 9: Oxidation of Sulfides and Sulfoxides

9.1: The First Example of Direct Oxidation of Sulfides to Sulfones by an Osmate– Molecular Oxygen System
B.M. Choudary, C. Reddy, V. Reddy, B.V. Prakash, M.L. Kantam and B. Sreedhar.

9.2: Selective Oxidation of Sulfides to Sulfoxides and Sulfones using Hydrogen Peroxide (H2O2) in the Presence of Zirconium Tetrachloride
K. Bahrami.

9.3: WO3–30% H2O2–Cinchona Alkaloids: a New Heterogeneous Catalytic System for Asymmetric Oxidation and Kinetic Resolution of Racemic Sulfoxides
V. V. Thakur and A. Sudalai.

9.4: Benzyl–4,6–isopropylidene–a–(D)–glucopyranoside, 2–deoxy–2–[[(2–hydroxy–3,5–di–tert–butylphenyl)methylene]amine] as a Ligand for Vanadium–Catalysed Asymmetric Oxidation of Sulfides
R. Del Litto, G. Roviello and F. Ruffo.

9.5: Asymmetric Sulfoxidation of Aryl Methyl Sulfides with H2O2 in Water
A. Scarso and G. Strukul

Blurb

Catalysts for Fine Chemical Synthesis

Series Editors: Eric Derouane (Universidade do Algarve, Faro, and Instituto Superior Tecnico, Lisbon, Portugal)

Ivan V. Kozhevnikov (University of Liverpool, UK)

Stanley M Roberts (University of Manchester, UK)

Catalysts are increasingly used by chemists engaged in fine chemical synthesis within both industry and academia. Today, there is a huge choice of high–tech catalysts that adds enormously to the repertoire of synthetic possibilities. However, catalysts are occasionally capricious, sometimes difficult to use and almost always require both skill and experience in order to achieve optimal results. This series offers practical help for advanced undergraduate, graduate and postgraduate students, as well as experienced chemists in industry and academia working with catalysts in organic and organometallic synthesis. It features tested and validated procedures, authoritative reviews on classes of catalysts, and assessments of all types of catalysts.

Catalysts for Fine Chemical Synthesis, Volume 5: Regio– and Stereo–Controlled Oxidations and Reductions

Editors: Stanley M. Roberts and John Whittall, (University of Manchester, UK)

Volume 5 in the series Catalysts for Fine Chemical Synthesis describes new procedures for the regio– and stereo–controlled transformations of compounds involving oxidation or reduction reactions. A wide range of catalysts are described, including organometallic systems, biocatalysts and biomimetics. Conversions that are discussed include:

• asymmetric hydrogenation of alkenes, enones, ene–esters and ene–acids
• asymmetric reduction of ketones
• imine reduction and reductive amination
• oxidation of primary and secondary alcohols
• hydroxylation, epoxidation and related reactions
• oxidation of ketones to lactones or enones
• oxidative C–C coupling
• oxidation of sulfides and sulfoxides

Regio– and Stereo–Controlled Oxidations and Reductions is a how–to practical guide with protocols detailed by the authors who have discovered the new transformations. The source of starting materials and reagents, hints, tips and safety advice (where appropriate) are given to ensure, as far as possible, that the procedures are reproducible. Comparisons to alternative methodology are given and relevant references to the primary literature are cited. In order to put the different procedures into proper context, the editors provide a short overview of recent developments in the field of oxidations and reductions.

This book is an important text for practising synthetic organic chemists in industry and academia.