Synthesis of Alcohols Introduction and Review

One of the reasons alcohols are important synthetic intermediates is that they can be synthesized directly from a wide variety of other functional groups. In Chapters 6 and 8, we examined the conversion of alkyl halides to alcohols by substitution and the conversion of alkenes to alcohols by hydration, hydroboration, and hydroxylation. These reactions are summarized here, with references for review if needed. 

Following this review, we will consider the largest and most versatile group of alcohol syntheses nucleophilic additions to carbonyl compounds. 

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Structure and Classification of Alcohols 425 10-3 Nomenclature of Alcohols and Phenols 427 10-4 Physical Properties of Alcohols 430 10-5 Commercially Important Alcohols 433 10-6 Acidity of Alcohols and Phenols 435 10-7 Synthesis of Alcohols Introduction and Review 438 Summary Previous Alcohol Syntheses 438 10-8 Organometallic Reagents for Alcohol Synthesis 440 10-9 Addition of Organometallic Reagents to Carbonyl Compounds 443... 

Many different substrates can undergo oxidative carbonylations, such as unsaturated and saturated hydrocarbons, aromatic and heteroaromatic derivatives, alcohols, phenols, and amines, giving a number of carbonyl compounds in a regio- and stereocontrolled fashion and with high degree of chemoselectivity. Oxidative car-bonylation reactions have been recently and carefully reviewed [10-13]. In this section a general overview of the most recent developments in oxidative carbonylations mediated by catalytic palladium(II) compounds and directed toward the synthesis of heterocyclic compounds is presented. As already reported in the introduction, the cyclocarbonylation reactions ending with the synthesis of simple lactones and lactams are reported in the chapter that discusses the carbonylation of alcohols and amines and are recently been reviewed [7,9,79]. 

Functionalization of hydrocarbons from petroleum sources is mainly concerned with the introduction of oxygen into the hydrocarbon molecule. In general, two ways are open to achieve oxygen functionalization oxidation and carbonylation. Oxidation is commonly encountered in the synthesis of aromatic acids, acrolein, maleic anhydride, ethene oxide, propene oxide, and acetaldehyde. Hydroformylation (CO/H2) (older literature and the technical literature refer to the oxo reaction) is employed for the large-scale preparation of butanol, 2-ethylhexanol, and detergent alcohols. The main use of 2-ethylhexanol is in phthalate esters which are softeners in PVC. The catalysts applied are based on cobalt and rhodium. (For a general review see ref. 3.)... 

Marine macrolides have numerous asymmetric centers, oxygenated function-ahties including alcohols, carbonyl groups, the tetrahydropyran moiety, di-and trisubstituted alkenes, and macrocycUc lactones. For completion of their total synthesis, efficient and stereoselective introduction of these characteristic units should be crucial. Recently, an excellent review on asymmetric synthesis of 1,3-diol, macrolactonization, and glycosidation in the syntheses of macrolides has been pubUshed by Nakata [5]. The multisubstituted tetrahydropyran moieties are often found in the marine macrohdes, and the efficient preparation of these moieties is recognized as the key reaction in their total synthesis. In this decade, efficient methods for their stereoselective construction have been developed and used in the total synthesis of marine macrolides, wherein the relative configuration of 2- and 6-substituents is pivotal. In this section, recent progress in the preparation of tetrahydropyrans is described (for a previous review on the preparation of tetrahydropyrans, see [9]). 

A review of synthetic methods for the most popular photoactive compounds used in diazoquinone resists—DNQ-5-sulfonate and DNQ-4-sulfonate—has been provided by Ershov et al. The synthesis typically begins with naphthalene derivatives, and proceeds via introduction of a sulfonic acid group, followed by diazotization and reaction with thionyl chloride to yield the sulfonic acid chloride (Scheme 7.2). In the next step, the chloride is reacted in a base-catalyzed esterification with a suitable ballast group or backbone, which usually is a multifunctional phenol, less frequently a monofunctional phenol or an aliphatic alcohol. ... 

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