Modern Gold Catalyzed Synthesis

by Hashmi, A. Stephen K.; Toste, F. Dean

• ISBN13: 9783527319527
• ISBN10: 3527319522
• Edition: 1st
• Format: Hardcover
• Copyright: 2012-05-21
• Publisher: Wiley-VCH

Summary

With its impressive features, gold has added another facet to organic catalysis. Focusing on homogeneous catalysis this book also covers the main applications in heterogeneous catalysis. Following a look at the gold-catalyzed addition of heteroatom nucleophiles to alkynes, this monograph goes on to discuss gold-catalyzed additions to allenes and alkenes, gold-catalyzed benzannulations, cycloisomerization and rearrangement reactions, as well as oxidation and reduction reactions. The whole is finished off with a section on gold-catalyzed aldol and related reactions and the application of gold-catalyzed reactions to natural product synthesis.

Author Biography

Stephen Hashmi is professor for Organic Chemistry at University of Heidelberg, Germany. He obtained his academic degrees from Ludwig-Maximilians-Universit?t M?nchen, after his postdoctoral studies with Barry M. Trost at Stanford University he started his Habilitation at Freie Universit?t Berlin with Johann Mulzer. During that time he followed Prof. Mulzer to Johann Wolfgang Goethe-Universit?t Franfurt and Universit?t Wien. He then returned to Frankfurt to finish his Habilitation. After the stations at University of Tasmania, Australia, Universit?t Marburg, and Universit?t Stuttgart, he was appointed a full professorship at Heidelberg University, where he is also involved in the Catalysis Research Laboratory (CaRLa). He received a number of awards, including a Karl-Zieger fellowship, the ORCHEM prize for natural scientists and the Hector research award.

F. Dean Toste was born in Terceira, Azores, Portugal but soon moved to Toronto Canada. He received his B.Sc. and M.Sc. degrees in chemistry from the University of Toronto, Canada where he worked with Prof. Ian W. J. Still. In 1995, he began his doctoral studies at Stanford
University under the direction of Professor Barry M. Trost. Following postdoctoral studies with Professor Robert H. Grubbs at Caltech, he joined the faculty at the University of California, Berkeley in 2002, and was promoted to Associate Professor in 2006 and Professor in 2009.
Professor Toste?s honors include an Alfred P. Sloan Research Fellowship, the Cope Scholar Award and the E. J. Corey Award from the American Chemical Society, BASF Catalysis Award, the OMCOS and Thieme Award from IUPAC, the Merck Award from the Royal Society of
Chemistry, the Mukaiyama Award, the Tetrahedron Young Investigator Award and numerous awards from the pharmaceutical industry.

Table of Contents

HYDROCHLORINATION OF ACETYLENE CATALYZED BY GOLD
Introduction
Reactions of Alkynes Using Gold Chloride as Catalyst
The Correlation of E88 with the Activity of Gold for the Hydrochlorination of Acetylene
Central Role of Au3 p and Regeneration of Au/C Catalysts
Reaction Mechanism of Alkynes Over Au/C Catalysts
Chemical Origin of the E8 Correlation and General Remarks
Commercial Processes and Economic Aspects of Vinyl Chloride Monomer Manufacture

GOLD-CATALYZED REDUCTION REACTIONS
Introduction
Hydrogenation of Multiple C?C Bonds. Role of the Gold Oxidation State
Hydrogenation of a,b-Unsaturated Aldehydes
Hydrogenation of Substituted Nitroaromatic Compounds

GOLD-CATALYZED BENZANNULATIONS: ASAO -
YAMAMOTO BENZOPYRYLIUM PATHWAY
Introduction
Acetylenic Compounds as 2p Systems
Enols as 2p Systems
Enol Ethers as 2p Systems
Benzynes as 2p Systems
Synthesis of Phthalazine Derivatives
Application to the Synthesis of Angucyclinone Antibiotics and Other Applications in Total Synthesis
Copper-Catalyzed Benzannulations
Conclusion

GOLD-CATALYZED REACTIONS OF PROPARGYL ESTERS, PROPARGYL ALCOHOLS, AND RELATED COMPOUNDS
Introduction and Extent of This Chapter
Propargyl Esters
Propargyl Ethers
Propargyl Alcohols
Propargyl Amines
Propargyl Carbonates, Amides, and Carbamates
Other Propargyl Substitution Patterns
Conclusion

INTRAMOLECULAR HYDROARYLATION OF ALKYNES
Introduction
Intramolecular Reactions of Arenes with Alkynes
Intramolecular Reactions of Electron-Rich Heteroarenes with Alkynes
Conclusion and Outlook

GOLD -
ALKYNE COMPLEXES
Introduction
Description of the M - p-Bond Interaction in Alkene and Alkyne Complexes
Gold(0) Complexes
Gold(I) Complexes
Gold(III) complexes
Theoretical Studies

GOLD -
ALKENE COMPLEXES
Introduction
Gold(0) Derivatives
Gold(I) Complexes
Gold(III) Complexes
Theoretical Studies

HYDRATION AND HYDROALKOXYLATION OF CC MULTIPLE BONDS
Historical Perspective
Gold Catalysts
Hydration and Hydroalkoxylation of CC Triple Bonds (Alkynes)
Hydration and Hydroalkoxylation of CC Double Bonds (Allenes and Alkenes)

GOLD-CATALYZED ALDOL AND RELATED REACTIONS
The Gold-Catalyzed Aldol Reaction
Related Reactions

GOLD-CATALYZED OXIDATION REACTIONS: OXIDATION OF ALKENES
Introduction
Epoxidation Reactions
Aziridination Reactions
Oxidative Cleavage of C?C Double Bonds
Oxygen Transfer to Carbenoids

GOLD-CATALYZED OXYGEN-ATOM TRANSFER TO ALKYNES
Introduction
Oxygen-Atom Transfer from NO Groups
Oxygen-Atom Transfer from Sulfoxides
Oxygen-Atom Transfer from Epoxides
Gold-Catalyzed Oxidative Coupling

GOLD-CATALYZED ADDITIONS TO ALKENES: N-NUCLEOPHILES

GOLD-CATALYZED ADDITIONS TO ALKENES: O-NUCLEOPHILES

OXIDATION OF ALCOHOLS AND CARBOHYDRATES
Introduction
Selective Oxidation of Alcohols
Selective Oxidation of Carbohydrates
Future Applications
Conclusion

APPLICATIONS OF GOLD-CATALYZED REACTIONS TO NATURAL PRODUCT SYNTHESIS
Introduction
Addition of Heteroatom Nucleophiles to Alkynes
Addition of Heteroatom Nucleophiles to Allenes
Cycloadditions via Pyrylium Intermediates from o-Alkynylacylarenes
Rearrangements of Propargyl Esters
Skeletal Rearrangement of 3-Butynyl-N-Oxides: (_)-Cermizine and (?)-Lentiginosine
Enyne Cyclizations
Propargyl Claisen Rearrangement: Azadirachtin
Gold-Catalyzed C?H Activation: (_)-Pterocarpan and Crassifolone
Gold-Catalyzed Allylic Amination: (_)-Angustureine
Catalytic Asymmetric Aldol Reaction of Isocyanoacetates and Aldehydes

GOLD-CATALYZED ADDITION REACTIONS TO ALLENES
Introduction
Addition of Heteroatom Nucleophiles
Addition of Carbon Nucleophiles
Conclusion