Asymmetric Hydrogenation and Transfer Hydrogenation

Virginie Ratovelomanana-Vidal, Phannarath Phansavath, Virginie Ratovelomanana-Vidal, Phannarath Phansavath

• Publisher: Wiley-VCH
• Year: 2021
• Print ISBN: 9783527346103
• eBook ISBN: 9783527822300
• Edition: 1
• Topic: Biological Sciences
• Subtopic: Biochemistry
• Index: Biological Sciences

Asymmetric Hydrogenation and Transfer Hydrogenation

Discover the latest developments in homogeneous asymmetric (transfer) hydrogenation with this up-to-date resource

Asymmetric Hydrogenation and Transfer Hydrogenation delivers a current and cutting-edge investigation of homogenous asymmetric hydrogenation and transfer hydrogenation reactions of prochiral substrates by using organometallic catalysts (like ruthenium, rhodium, iridium, iron, and copper) and organic catalysts.

Distinguished researchers and editors Virginie Ratovelomanana-Vidal and Phannarath Phansavath also offer readers a comprehensive walkthrough of substituted ketones through dynamic kinetic resolution, as well a presentation of the mechanisms and application of asymmetric hydrogenation reactions to the synthesis of biologically relevant compounds.

The book comprehensively details its complex subject matter clearly and plainly and covers everything from catalyst development and reactions to mechanisms and applications in academia and industry. The papers included within come from many of the leading voices in their respective fields and represent the newest and best research available today.

Compiled for researchers and private-industry chemists alike, Asymmetric Hydrogenation and Transfer Hydrogenation also discusses a wide variety of other topics like:

• A discussion of the development of chiral metal catalysts for asymmetric transfer hydrogenation
• Several examinations of asymmetric transfer hydrogenation of a variety of chemical groups, including ketones, aryl and heteroaryl ketones, substituted ketones, and heteroaromatic compounds, alkenes, and imines
• An exploration of the mechanism of asymmetric hydrogenation and continuous flow asymmetric hydrogenation
• A full and thorough treatment of the industrial applications of asymmetric hydrogenation

Perfect for catalytic chemists, chemists working on or with organometallics, organic chemists, natural product chemists, pharmaceutical chemists, medicinal chemists, and industrial chemists, Asymmetric Hydrogenation and Transfer Hydrogenation also belongs on the bookshelves of research and university institutes and libraries who wish to expand their selection on a topic fundamental to organic synthesis.

1
The Historical Development of Asymmetric Hydrogenation

John M. Brown

Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK

1.1 Introduction

How did chemists gain the current levels of knowledge and expertise for controlling molecular chirality through hydrogenation or otherwise? The desirability of asymmetric synthesis was recognized in the 1880s by Emil Fischer and others, but practical solutions only arose more than 80 years later. The key reasons are explored here. This brief review has five main Sections 1.2–1.6, covering first the development of ideas underpinning our understanding of asymmetry, then the initial applications to asymmetric synthesis, and also the development of asymmetric heterogeneous hydrogenation of alkenes. The final sections on asymmetric homogeneous hydrogenation of alkenes are limited to work published in or before the early 1980s, in advance of extensive developments, and thus excluding the important inputs of iridium catalysts and more recently early transition metals.

1.2 Early Work on the Recognition of Molecular Asymmetry

Chemistry was an emerging science by the beginning of the nineteenth century with many opportunities for fundamental discovery. At that time scientists crossed disciplines easily; optics and mineralogy played important roles because of the ready accessibility and verifiable purity of solid substances. Malus had invented the first polarimeter in 1808, enabling measurement of both the sense and magnitude of rotation of plane‐polarized light [4]. Following this, work by Arago and others on the interaction of polarized light with minerals intensified in the following decade [5]. Haüy had earlier concluded that each type of crystal has a fundamental primitive, nucleus or “integrant molecule” of a particular shape, that could not be broken further without destroying both the physical and chemical nature of the crystal. He had accidentally dropped and shattered a crystal of calcite that enabled him to make the deduction [6]. Biot observed the striking phenomenon that samples of plane sections of rock crystal (α‐quartz) rotated the plane of plane‐polarized light. Furthermore, some quartz crystals rotated polarized light to the right, and others to the left. The observations obtained by Biot for liquids in his designed polarimeter showed that diverse natural substances, either as liquids or in solution, showed the same phenomenon of optical activity with consistent rotations to the left or to the right for a given substance, which he quantified through Biot’s Law. The vapor of oil of turpentine also demonstrated optical activity. By contrast, water, alcohol, and sulfuric acid were inactive [7, 8]. Biot deduced that the response to polarized light was a property exhibited by the individual molecules of the analyte, making a link to Haüy’s proposal. The English scientist Herschel was aware of this work and was able to correlate the direction of rotation for α‐quartz crystals with the structure of the crystal. He made it clear that the mirror‐image pair differed by virtue of the hemihedral faces that were themselves object and mirror image (Figure 1.1) [1, 2]. Well over a 100 years then elapsed before the absolute configuration of an α‐quartz crystal was determined by De Vries DeVries, using Bijvoet’s recently developed anomalous dispersion method. The laevorotatory form is on the left of Figure 1.1a [3].

Figure 1.1 α‐quartz crystals with object and mirror image hemihedral faces; inner part shows packing of sub‐units. Created by K‐H Ernst and reproduced with permission of Wiley‐VCH.

This laid the groundwork for explaining a puzzling observation. Cream of Tartar is a crystalline product isolated as a by‐product from winemaking and was widely used in baking and otherwise. It was known to be the dipotassium salt of tartaric acid and showed an optical rotation as expected. A winemaker in the Vosges had isolated a second crystalline product at the same stage of production, and the ensuing isolated acid (racemic acid) had similar properties to tartaric acid but lacked optical activity. This became interesting to the prominent Swedish chemist Berzelius in the late 1820s [9]. He characterized his “paratartaric acid” thoroughly. It was identical to tartaric acid in analytical composition, had the same chemical composition and the same physical properties, and same distinct melting points. His student Mitscherlich [10], by then working in Berlin, discovered that an aqueous solution of paratartaric acid was “indifferent” to polarized light in contrast to the known optical activity of tartaric acid and its salts in solution, although his isolated crystal was active. From th...

Table of contents

• Cover
• Table of Contents
• Title Page
• Copyright
• Foreword
• Preface
• 1 The Historical Development of Asymmetric Hydrogenation
• 2 Asymmetric (Transfer) Hydrogenation of Functionalized Alkenes During the Past Decade
• 3 Asymmetric (Transfer) Hydrogenation of Functionalized Ketones
• 4 Asymmetric (Transfer) Hydrogenation of Aryl and Heteroaryl Ketones
• 5 Asymmetric (Transfer) Hydrogenation of Substituted Ketones Through Dynamic Kinetic Resolution
• 6 Industrial Applications of Asymmetric (Transfer) Hydrogenation
• 7 Tethered Ruthenium(II) Catalysts in Asymmetric Transfer Hydrogenation
• 8 Homogeneous Asymmetric Hydrogenation of Heteroaromatic Compounds Catalyzed by Transition Metal Complexes
• 9 Asymmetric (Transfer) Hydrogenation of Imines
• 10 Asymmetric Hydrogenation in Continuous‐Flow Conditions
• 11 Organocatalytic Asymmetric Transfer Hydrogenation Reactions
• Index
• End User License Agreement